Diazirine compounds and compositions derived therefrom

ABSTRACT

A series of diazirine compounds of formula (I) having utility as photocrosslinkers are disclosed. 
     
       
         
         
             
             
         
       
     
     Where, A, L, z, Ar x  and R y  are as defined herein. Also disclosed are the photodefinable compositions containing these compounds.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/053,921, filed Sep. 23, 2014, which is incorporated herein byreference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a series of diazirine compounds. Morespecifically, the present invention relates to a series ofbis-diazirines, tris-diazirines and tetrakis-diazirines, and the like,having utility as photocrosslinkers. This invention also relates tophotodefinable compositions containing these diazirine compounds.

2. Description of the Art

There has been a growing interest in developing new electronic materialsfeaturing superior chemical, optical and mechanical properties, whichare environmentally friendly and can be processed under aqueousconditions. Most notably, there is a growing demand for developingmaterials which are capable of forming micron-level structures. Inparticular, micron-level device geometries have become common place inthe fabrication of a variety of liquid crystal displays (LCDs), organiclight emitting diodes (OLEDs) and other radio frequency (RF) andmicrowave devices. For example, devices such as radio frequencyintegrated circuits (RFICs), micro-machine integrated circuits (MMICs),switches, couplers, phase shifters, surface acoustic wave (SAW) filtersand SAW duplexers, have recently been fabricated in the micron-levels.

In addition, there has been growing interest in organic electronic (OE)devices, for example, organic field effect transistors (OFET) for use inbackplanes of display devices or logic capable circuits, and organicphotovoltaic (OPV) devices, among others. A conventional OFET has a gateelectrode, a gate insulator layer made of a dielectric material (alsoreferred to as “dielectric” or “gate dielectric”), source and drainelectrodes, a semiconducting layer made of an organic semiconductor(OSC) material, and typically a passivation layer on top of theaforementioned layers to provide protection against environmentalinfluence or against damage from subsequent device manufacturing steps.

In most electronic and optoelectronic devices, the OSC material employedmust feature certain requisite properties including low permittivity(“low-k”), non-charge trapping, and orthogonality to other organicmaterials used therewith. In addition, there is also a need for goodcross-linking functionality which often is difficult to incorporatewithout modifying the low permittivity. The current materials alsoemploy a variety of fluorinated solvents which are not onlyenvironmentally unfriendly but also not cost effective.

Accordingly, it is an object of this invention to provide a series ofbis-diazirines, tris-diazirines and tetrakis-diazirines, and the like,which are found to be effective photocrosslinkers.

It is also an object of this invention to provide a variety ofphotoimageable compositions, which can be used in a variety ofapplications including in the fabrication of electronic, optoelectronicdevices.

Other objects and further scope of the applicability of the presentinvention will become apparent from the detailed description thatfollows.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that certain of the bis-diazirines,tris-diazirines or tetrakis-diazirines, when suitably exposed toradiation releases dinitrogen forming a reactive carbene intermediate,which aspect can be exploited to make photoimageable compositions. Thehighly active carbene thus formed in situ can insert (i.e., react) intoone or more other materials either via inserting into an OH, NH, CH orolefin functionality of such materials or other functionality that maybe present to form the cross-linked insertion product. Thus, a compoundhaving two or more diazirine functionalities (i.e., bis- ortris-diazirines, etc.) would have the ability to crosslink one or morematerials, such as the polymeric materials used in the fabrication ofelectronic or optoelectronic devices as described herein. It has beenreported that certain compounds which can generate nitrene intermediatescan be used in the fabrication of such electronic and/or optoelectronicdevices. Thus, it is envisioned that the compounds of this invention aremore suitable for such application as they may feature even lowerpermittivity properties (lower k due to no heteroatom) than thecorresponding nitrene generating compounds but also may provide highercross-linking capability as a carbene is expected to be more reactivethan a nitrene. It is further expected that the nitrene inserted productresults in an amine which can be a source for charge trapping, whereascarbene inserted product produces no such product. It should further benoted that the commonly known carbene precursors such as certain diazocompounds are unstable, however, the bis-(diazirines), tris-(diazirines)and tetrakis-(diazirines) as disclosed herein are stable compounds.

Accordingly, there is provided a compound of the formula (I):

Wherein, A is a carbon, silicon, oxygen or nitrogen central core moiety;

L is a bond or a divalent linking or a spacer group selected from ether,ketone, amine, sulfide, sulfone, ester, amide or a combination thereof;Ar_(x) is an aromatic or heteroaromatic group and R_(y) is an alkyl,aryl, arylalkyl, partly fluorinated or perfluorinated alkyl, aryl andarylalkyl group; and z is an integer from 2 to 4. Non-limiting examplesof central core moiety A can be selected from aliphatic, cycloaliphatic,heteroaliphatic, heterocycloaliphatic, aromatic or heteroaromaticmoieties.

In another aspect there is provided a compound of formula (IA):

Wherein,

L is a bond or a divalent linking or a spacer group selected from:

—C(O)O—R₄—OC(O)—, —C(O)O—R₄—, —R₄—OC(O)—R₄—, —C(O)—R₄—OC(O)—, —C(O)—R₄—,—R₄—C(O)—R₄—, —O—R₄—OC(O)—, —O—R₄—O—, —O—R₄—, —R₄—O—R₄—,—C(O)NR₅—R₄—OC(O)—, —C(O)NR₅—R₄—NR₅C(O)—, —C(O)NR₅—R₄—, —R₄—NR₅C(O)—R₄—,—C(O)—R₄—NR₅C(O)—, —NR₅—R₄—OC(O)—, —NR₅—R₄—NR₅C(O)—, —NR₅—R₄—,—R₄—NR₅—R₄—, —NR₅—R₄—NR₅—

and —R₄—, where each occurrence of R₄ may be the same or different whichis a divalent group independently selected from (C₁-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)aryl, (C₆-C₁₂)aryl(C₁-C₁₂)alkyl,(C₆-C₁₀)heteroaryl, (C₆-C₁₀)heteroaryl(C₁-C₁₂)alkyl, —(CH₂—CH₂—O)_(a)—,where a is an integer from 1 to 10, provided that when R₄ is—(CH₂—CH₂—O)_(a)— then the oxygen end of said group is linked only witheither carbon or silicon containing linking group, which are optionallysubstituted with a group selected from halogen, —OH, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₀)aryloxy, (C₆-C₁₂)aralkyl and(C₆-C₁₂)aralkyloxy; and R₅ is hydrogen, (C₁-C₆)alkyl, (C₆-C₁₀)aryl or(C₆-C₁₀)aralkyl;

R₁ and R₂ are the same or different and each is independently selectedfrom (C₁-C₁₂)alkyl, where portions of hydrogen on alkyl are replacedwith fluorine, (C₁-C₁₂)perfluoroalkyl, (C₆-C₁₂)aryl,(C₆-C₁₂)aryl(C₁-C₁₂)alkyl, where portions of hydrogen on alkyl arereplaced with fluorine, and (C₆-C₁₂)arylperfluoro(C₁-C₁₂)alkyl; and

Ar₁ and Ar₂ are the same or different and each is independently selectedfrom (C₆-C₁₂)arylene or (C₆-C₁₂)heteroarylene group optionallysubstituted with a group selected from halogen, —OH, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₂)aryloxy, (C₆-C₁₂)aryl(C₁-C₄)alkyland (C₆-C₁₂)aryl(C₁-C₄)alkyloxy; and

with the proviso that the following compounds are excluded:

where n is 7 or 12; and

where n′ is 3 or 5.

In another aspect of this invention there is also provided a compound offormula (II) or (IIA):

Where L, A, Ar₁, Ar₂, R₁ and R₂ are as defined herein. Ar₃ and Ar_(3a)may be the same as Ar₁ and Ar₂ and are independently of each otherselected from (C₆-C₁₂)arylene or (C₆-C₁₂)heteroarylene group optionallysubstituted with a group selected from halogen, —OH, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₂)aryloxy, (C₆-C₁₂)aryl(C₁-C₄)alkyland (C₆-C₁₂)aryl(C₁-C₄)alkyloxy. Similarly, R₃ and R_(3a) may be thesame as R₁ and R₂ and are independently of each other selected from(C₁-C₁₂)alkyl, where portions of hydrogen on alkyl are replaced withfluorine, (C₁-C₁₂)perfluoroalkyl, (C₆-C₁₂)aryl,(C₆-C₁₂)aryl(C₁-C₁₂)alkyl, where portions of hydrogen on alkyl arereplaced with fluorine, and (C₆-C₁₂)arylperfluoro(C₁-C₁₂)alkyl.

In another aspect of this invention there is also provided aphotoimageable composition comprising:

a polymer capable of reacting with a carbene to form a carbene insertedproduct;

a compound of the formula (IA), (II) or (IIA):

wherein,

L is a divalent linking or a spacer group selected from:

—C(O)O—R₄—OC(O)—, —C(O)O—R₄—, —R₄—OC(O)—R₄—, —C(O)—R₄—OC(O)—, —C(O)—R₄—,—R₄—C(O)—R₄—, —O—R₄—OC(O)—, —O—R₄—O—, —O—R₄—, —R₄—O—R₄—,—C(O)NR₅—R₄—OC(O)—, —C(O)NR₅—R₄—NR₅C(O)—, —C(O)NR₅—R₄—, —R₄—NR₅C(O)—R₄—,—C(O)—R₄—NR₅C(O)—, —NR₅—R₄—OC(O)—, —NR₅—R₄—NR₅C(O)—, —NR₅—R₄—,—R₄—NR₅—R₄—, —NR₅—R₄—NR₅—, —R₄—, and

where each occurrence of R₄ may be the same or different which is adivalent group independently selected from (C₁-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)aryl, (C₆-C₁₂)aryl(C₁-C₁₂)alkyl,(C₆-C₁₀)heteroaryl, (C₆-C₁₀)heteroaryl(C₁-C₁₂)alkyl, —(CH₂—CH₂—O)_(a)—,where a is an integer from 1 to 10, provided that when R₄ is—(CH₂—CH₂—O)_(a)— then the oxygen end of said group is linked only witheither carbon or silicon containing linking group, which are optionallysubstituted with a group selected from halogen, —OH, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₀)aryloxy, (C₆-C₁₂)aralkyl and(C₆-C₁₂)aralkyloxy; and R₅ is hydrogen, (C₁-C₆)alkyl, (C₆-C₁₀)aryl or(C₆-C₁₀)aralkyl;

A is a carbon, silicon, oxygen or nitrogen central core moiety;

R₁, R₂, R₃ and R_(3a) are the same or different and each isindependently selected from (C₁-C₁₂)alkyl, where portions of hydrogen onalkyl are replaced with fluorine, (C₁-C₁₂)perfluoroalkyl, (C₆-C₁₂)aryl,(C₆-C₁₂)aryl(C₁-C₁₂)alkyl, where portions of hydrogen on alkyl arereplaced with fluorine, and (C₆-C₁₂)arylperfluoro(C₁-C₁₂)alkyl; and

Ar₁, Ar₂ and Ar₃ are the same or different and each is independentlyselected from (C₆-C₁₂)arylene or (C₆-C₁₂)heteroarylene group optionallysubstituted with a group selected from halogen, —OH, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₂)aryloxy, (C₆-C₁₂)aryl(C₁-C₄)alkyland (C₆-C₁₂)aryl(C₁-C₄)alkyloxy; and

a carrier solvent.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments in accordance with the present invention are described belowwith reference to the following accompanying figures and/or images.Where drawings are provided, it will be drawings which are simplifiedportions of various embodiments of this invention and are provided forillustrative purposes only.

FIG. 1 is a lithographic image obtained for the composition of thisinvention containing the polymer, poly(HexNB) as set forth in Example 3and the diazirine as set forth in Example 2.

FIG. 2 is a lithographic image obtained for the composition of thisinvention containing the polymer, ZEONEX® 480R (a commercially availablecyclo olefin polymer from Zeon Corporation, Tokyo, Japan) and thediazirine as set forth in Example 2.

FIG. 3 is a lithographic image obtained for the composition of thisinvention containing the polymer, TOPAS® 6013S-04 (a commerciallyavailable cyclo olefin polymer from Topas Advanced Polymers, Inc.,Florence, Ky., USA) and the diazirine as set forth in Example 2.

FIG. 4 is a lithographic image obtained for the composition of thisinvention containing the NB/NBSiMe₂(OEt) copolymer as set forth inExample 4 and the diazirine as set forth in Example 2.

DETAILED DESCRIPTION

The terms as used herein have the following meanings:

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the claimsappended hereto, are subject to the various uncertainties of measurementencountered in obtaining such values, unless otherwise indicated, allare to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous,inclusive of both the minimum and maximum values of the range as well asevery value between such minimum and maximum values. Still further,where a range refers to integers, every integer between the minimum andmaximum values of such range is included. In addition, where multipleranges are provided to describe a feature or characteristic, such rangescan be combined. That is to say that, unless otherwise indicated, allranges disclosed herein are to be understood to encompass any and allsub-ranges subsumed therein. For example, a stated range of from “1 to10” should be considered to include any and all sub-ranges between theminimum value of 1 and the maximum value of 10. Exemplary sub-ranges ofthe range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8,and 5.5 to 10, etc.

As used herein, the symbol “

” denotes a position at which the bonding takes place with anotherrepeat unit or another atom or molecule or group or moiety asappropriate with the structure of the group as shown.

As used herein, “hydrocarbyl” refers to a group that contains carbon andhydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl,aralkyl, alkaryl, and alkenyl. The term “halohydrocarbyl” refers to ahydrocarbyl group where at least one hydrogen has been replaced by ahalogen. The term perhalocarbyl refers to a hydrocarbyl group where allhydrogens have been replaced by a halogen.

As used herein, the expression “(C₁-C₆)alkyl” includes methyl and ethylgroups, and straight-chained or branched propyl, butyl, pentyl and hexylgroups. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyland tert-butyl. Derived expressions such as “(C₁-C₄)alkoxy”,“(C₁-C₄)thioalkyl” “(C₁-C₄)alkoxy(C₁-C₄)alkyl”, “hydroxy(C₁-C₄)alkyl”,“(C₁-C₄)alkylcarbonyl”, “(C₁-C₄)alkoxycarbonyl(C₁-C₄)alkyl”,“(C₁-C₄)alkoxycarbonyl”, “amino(C₁-C₄)alkyl”, “(C₁-C₄)alkylamino”,“(C₁-C₄)alkylcarbamoyl(C₁-C₄)alkyl”,“(C₁-C₄)dialkylcarbamoyl(C₁-C₄)alkyl” “mono- ordi-(C₁-C₄)alkylamino(C₁-C₄)alkyl”, “amino(C₁-C₄)alkylcarbonyl”“diphenyl(C₁-C₄)alkyl”, “phenyl(C₁-C₄)alkyl”,“phenylcarboyl(C₁-C₄)alkyl” and “phenoxy(C₁-C₄)alkyl” are to beconstrued accordingly.

As used herein, the expression “cycloalkyl” includes all of the knowncyclic groups. Representative examples of “cycloalkyl” includes withoutany limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, and the like. Derived expressions such as“cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl”are to be construed accordingly.

As used herein, the expression “(C₂-C₆)alkenyl” includes ethenyl andstraight-chained or branched propenyl, butenyl, pentenyl and hexenylgroups. Similarly, the expression “(C₂-C₆)alkynyl” includes ethynyl andpropynyl, and straight-chained or branched butynyl, pentynyl and hexynylgroups.

As used herein the expression “(C₁-C₄)acyl” shall have the same meaningas “(C₁-C₄)alkanoyl”, which can also be represented structurally as“R—CO—,” where R is a (C₁-C₃)alkyl as defined herein. Additionally,“(C₁-C₃)alkylcarbonyl” shall mean same as (C₁-C₄)acyl. Specifically,“(C₁-C₄)acyl” shall mean formyl, acetyl or ethanoyl, propanoyl,n-butanoyl, etc. Derived expressions such as “(C₁-C₄)acyloxy” and“(C₁-C₄)acyloxyalkyl” are to be construed accordingly.

As used herein, the expression “(C₁-C₆)perfluoroalkyl” means that all ofthe hydrogen atoms in said alkyl group are replaced with fluorine atoms.Illustrative examples include trifluoromethyl and pentafluoroethyl, andstraight-chained or branched heptafluoropropyl, nonafluorobutyl,undecafluoropentyl and tridecafluorohexyl groups. Derived expression,“(C₁-C₆)perfluoroalkoxy”, is to be construed accordingly. It shouldfurther be noted that certain of the alkyl groups as described herein,such as for example, “(C₁-C₆)alkyl” may partially be fluorinated, thatis, only portions of the hydrogen atoms in said alkyl group are replacedwith fluorine atoms and shall be construed accordingly.

As used herein, the expression “(C₆-C₁₀)aryl” means substituted orunsubstituted phenyl or naphthyl. Specific examples of substitutedphenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl,1-methylnaphthyl, 2-methylnaphthyl, etc. “Substituted phenyl” or“substituted naphthyl” also include any of the possible substituents asfurther defined herein or one known in the art. Derived expression,“(C₆-C₁₀)arylsulfonyl,” is to be construed accordingly.

As used herein, the expression “(C₆-C₁₀)aryl(C₁-C₄)alkyl” means that the(C₆-C₁₀)aryl as defined herein is further attached to (C₁-C₄)alkyl asdefined herein. Representative examples include benzyl, phenylethyl,2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.

As used herein, the expression “heteroaryl” includes all of the knownheteroatom containing aromatic radicals. Representative 5-memberedheteroaryl radicals include furanyl, thienyl or thiophenyl, pyrrolyl,isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl,and the like. Representative 6-membered heteroaryl radicals includepyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the likeradicals. Representative examples of bicyclic heteroaryl radicalsinclude, benzofuranyl, benzothiophenyl, indolyl, quinolinyl,isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl,pyridothienyl, and the like radicals.

As used herein, the expression “heterocycle” includes all of the knownreduced heteroatom containing cyclic radicals. Representative 5-memberedheterocycle radicals include tetrahydrofuranyl, tetrahydrothiophenyl,pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl,and the like. Representative 6-membered heterocycle radicals includepiperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like.Various other heterocycle radicals include, without limitation,aziridinyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]hept-2-yl, andtriazocanyl, and the like.

“Halogen” or “halo” means chloro, fluoro, bromo, and iodo.

In a broad sense, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a few of the specificembodiments as disclosed herein, the term “substituted” meanssubstituted with one or more substituents independently selected fromthe group consisting of C₁₋₆ alkyl, C₂₋₆alkenyl, C₁₋₆perfluoroalkyl,phenyl, hydroxy, —CO₂H, an ester, an amide, C₁-C₆alkoxy, C₁-C₆thioalkyl,C₁-C₆perfluoroalkoxy, —NH₂, Cl, Br, I, F, —NH-lower alkyl, and —N(loweralkyl)₂. However, any of the other suitable substituents known to oneskilled in the art can also be used in these embodiments.

It should be noted that any atom with unsatisfied valences in the text,schemes, examples and tables herein is assumed to have the appropriatenumber of hydrogen atom(s) to satisfy such valences.

As used herein, the terms “orthogonal” and “orthogonality” will beunderstood to mean chemical orthogonality. For example, an orthogonalsolvent means a solvent which, when used in the deposition of a layer ofa material dissolved therein on a previously deposited layer, does notdissolve said previously deposited layer.

As used herein, the term “organic semiconductor (OSC) composition”, alsoshortly referred to as “composition”, means at least one organicsemiconductor (OSC) compound and one or more other materials added tothe at least one OSC compound to provide, or to modify, specificproperties of the OSC composition and/or of the at least one OSCcompound therein. It will be understood that an OSC composition is alsoa vehicle for carrying the OSC to a substrate to enable the forming oflayers or structures thereon. Exemplary materials include, but are notlimited to, solvents, volatile surfactants and adhesion promoters.

As used herein, the terms “polymer composition,” “copolymercomposition,” “terpolymer composition” or “tetrapolymer composition” areused herein interchangeably and are meant to include at least onesynthesized polymer, copolymer, terpolymer or tetrapolymer, as well asresidues from initiators, solvents or other elements attendant to thesynthesis of such polymers, where such residues are understood as notnecessarily being covalently incorporated thereto. But some catalysts orinitiators may sometimes be covalently bound to a part of the polymericchain either at the beginning and/or end of the polymeric chain. Suchresidues and other elements considered as part of the “polymer” or“polymer composition” are typically mixed or co-mingled with the polymersuch that they tend to remain therewith when it is transferred betweenvessels or between solvent or dispersion media. A polymer compositioncan also include materials added after synthesis of the polymer toprovide or modify specific properties of such composition. Suchmaterials include, but are not limited to solvent(s), antioxidant(s),photoinitiator(s), sensitizers and other materials as will be discussedmore fully below.

By the term, “a monomer repeat unit is derived” is meant that thepolymeric repeating units are polymerized (formed) from, e.g.,polycyclic norbornene-type monomers, wherein the resulting polymers areformed by 2,3 enchainment of norbornene-type monomers as shown below:

Thus, in accordance with the practice of this invention there isprovided a compound of the formula (I):

Wherein, A is a carbon, silicon, oxygen or nitrogen central core moiety;

L is a bond or a divalent linking or a spacer group selected from ether,ketone, amine, sulfide, sulfone, ester, amide or a combination thereof;Ar_(x) is an aromatic or heteroaromatic group and R_(y) is an alkyl,aryl, arylalkyl, partly fluorinated or perfluorinated alkyl, aryl andarylalkyl group; and z is an integer from 2 to 4. Non-limiting examplesof central core moiety A can be selected from aliphatic, cycloaliphatic,heteroaliphatic, heterocycloaliphatic, aromatic or heteroaromaticmoieties.

In another aspect there is provided a compound of formula (IA):

Wherein,

L is a bond or a divalent linking or a spacer group selected from:

—C(O)O—R₄—OC(O)—, —C(O)O—R₄—, —R₄—OC(O)—R₄—, —C(O)—R₄—OC(O)—, —C(O)—R₄—,—R₄—C(O)—R₄—, —O—R₄—OC(O)—, —O—R₄—O—, —O—R₄—, —C(O)NR₅—R₄—OC(O)—,—C(O)NR₅—R₄—NR₅C(O)—, —C(O)NR₅—R₄—, —R₄—NR₅C(O)—R₄—, —C(O)—R₄—NR₅C(O)—,—NR₅—R₄—OC(O)—, —NR₅—R₄—NR₅C(O)—, —NR₅—R₄—, —R₄—NR₅—R₄—, —NR₅—R₄—NR₅—

and —R₄—, where each occurrence of R₄ may be the same or different whichis a divalent group independently selected from (C₁-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)aryl, (C₆-C₁₂)aryl(C₁-C₁₂)alkyl,(C₆-C₁₀)heteroaryl,(C₆-C₁₀)heteroaryl(C₁-C₁₂)alkyl, —(CH₂—CH₂—O)_(a)—, where a is aninteger from 1 to 10, provided that when R₄ is —(CH₂—CH₂—O)_(a)— thenthe oxygen end of said group is linked only with either carbon orsilicon containing linking group, which are optionally substituted witha group selected from halogen, —OH, (C₁-C₄)alkyl, (C₁-C₄)alkoxy,(C₆-C₁₀)aryl, (C₆-C₁₀)aryloxy, (C₆-C₁₂)aralkyl and (C₆-C₁₂)aralkyloxy;and R₅ is hydrogen, (C₁-C₆)alkyl, (C₆-C₁₀)aryl or (C₆-C₁₀)aralkyl;

R₁ and R₂ are the same or different and each is independently selectedfrom (C₁-C₁₂)alkyl, where portions of hydrogen on alkyl are replacedwith fluorine, (C₁-C₁₂)perfluoroalkyl, (C₆-C₁₂)aryl,(C₆-C₁₂)aryl(C₁-C₁₂)alkyl, where portions of hydrogen on alkyl arereplaced with fluorine, and (C₆-C₁₂)arylperfluoro(C₁-C₁₂)alkyl; and

Ar₁ and Ar₂ are the same or different and each is independently selectedfrom (C₆-C₁₂)arylene or (C₆-C₁₂)heteroarylene group optionallysubstituted with a group selected from halogen, —OH, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₂)aryloxy, (C₆-C₁₂)aryl(C₁-C₄)alkyland (C₆-C₁₂)aryl(C₁-C₄)alkyloxy; and

with the proviso that the following compounds are excluded:

where n is 7 or 12; and

where n′ is 3 or 5.

In another aspect of this invention there is also provided a compound offormula (II) or (IIA):

Where L, A, Ar₁, Ar₂, R₁ and R₂ are as defined herein. Ar₃ and Ar_(3a)may be the same as Ar₁ and Ar₂ and are independently of each otherselected from (C₆-C₁₂)arylene or (C₆-C₁₂)heteroarylene group optionallysubstituted with a group selected from halogen, —OH, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₂)aryloxy, (C₆-C₁₂)aryl(C₁-C₄)alkyland (C₆-C₁₂)aryl(C₁-C₄)alkyloxy. Similarly, R₃ and R_(3a) may be thesame as R₁ and R₂ and are independently of each other selected from(C₁-C₁₂)alkyl, where portions of hydrogen on alkyl are replaced withfluorine, (C₁-C₁₂)perfluoroalkyl, (C₆-C₁₂)aryl,(C₆-C₁₂)aryl(C₁-C₁₂)alkyl, where portions of hydrogen on alkyl arereplaced with fluorine, and (C₆-C₁₂)arylperfluoro(C₁-C₁₂)alkyl.

As noted above, a few of the compounds of formula (I) are known in theliterature and such compounds are excluded from this aspect of theinvention. For example, K. Simonton et al., RadTech e/5, 2006, TechnicalProceedings, disclose a bifunctional diazirine of formula:

Propane-1,3-diyl bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate).Similarly, H. Mehenni et al., Aust. J. Chem. 2012, 65, 193-201, disclosea series of bis(diazirines) including the bis(diazirine) diamides offormula:

where n is 7 or 12;As well as well as some of the amido ethers of formula:

where n is 3 or 5.Accordingly, the above noted compounds are excluded from this invention.

In one of the embodiments of this invention, the compound of the formula(IA), (II) or (IIA) encompasses the following:

-   -   L is a linking group selected from:        -   —C(O)O—(CH₂)_(b)—O(CO)—, —C(O)O—(CH₂)_(b)—,            —(CH₂)_(b)—O(CO)—(CH₂)_(b)—, —C(O)—(CH₂)_(b)—O(CO)—,            —C(O)—(CH₂)_(b)—, —(CH₂)_(b)—(CO)—(CH₂)_(b)—,            —O—(CH₂)_(b)—O(CO)—, —O—(CH₂)_(b)—O—, —O—(CH₂)_(b)—,            —(CH₂)_(b)—O—(CH₂)_(b)—, —C(O)NR₅—(CH₂)_(b)—O(CO)—,            —C(O)NR₅—(CH₂)_(b)—NR₅(CO)—, —C(O)NR₅—(CH₂)_(b)—,            —(CH₂)_(b)—NR₅(CO)—(CH₂)_(b)—, —C(O)—(CH₂)_(b)—NR₅(CO)—,            —NR₅—(CH₂)_(b)—O(CO)—, —NR₅—(CH₂)_(b)—NR₅(CO)—,            —NR₅—(CH₂)_(b)—, —(CH₂)_(b)—NR₅—(CH₂)_(b)—,            —NR₅—(CH₂)_(b)—NR₅— where b is an integer from 1 to 12; R₅            is hydrogen, (C₁-C₄)alkyl, phenyl, naphthyl, tolyl or            benzyl;    -   R₁, R₂, R₃ and R_(3a) are the same or different and each        independently selected from (C₁-C₆)alkyl, (C₁-C₆)perfluoroalkyl,        (C₆-C₈)aryl, (C₆-C₈)perfluoroaryl, (C₆-C₁₀)aralkyl or        (C₆-C₁₀)perfluoroarylperfluoroalkyl; and    -   Ar₁, Ar₂, Ar₃ and Ar_(3a) are the same or different and are        independently of each other selected from phenylene or        naphthalene group optionally substituted with a group selected        from halogen, —OH, (C₁-C₄)alkyl, (C₁-C₄)alkoxy, (C₆-C₁₀)aryl,        (C₆-C₁₀)aryloxy, (C₆-C₁₂)aralkyl and (C₆-C₁₂)aralkyloxy.

In one of the embodiments of this invention, the compound of the formula(II) or (IIA) encompasses the following:

-   -   L is a linking group selected from:        -   —C(O)O—(CH₂)_(b)—O(CO)—, —C(O)O—(CH₂)_(b)—,            —(CH₂)_(b)—O(CO)—(CH₂)_(b)—, —C(O)—(CH₂)_(b)—O(CO)—,            —C(O)—(CH₂)_(b)—, —(CH₂)_(b)—(CO)—(CH₂)_(b)—,            —O—(CH₂)_(b)—O(CO)—, —O—(CH₂)_(b)—O—, —O—(CH₂)_(b)—,            —(CH₂)_(b)—O—(CH₂)_(b)—, —C(O)NR₅—(CH₂)_(b)—O(CO)—,            —C(O)NR₅—(CH₂)_(b)—NR₅(CO)—, —C(O)NR₅—(CH₂)_(b)—,            —(CH₂)_(b)—NR₅(CO)—(CH₂)_(b)—, —C(O)—(CH₂)_(b)—NR₅(CO)—,            —NR₅—(CH₂)_(b)—O(CO)—, —NR₅—(CH₂)_(b)—NR₅(CO)—,            —NR₅—(CH₂)_(b)—, —(CH₂)_(b)—NR₅—(CH₂)_(b)—,            —NR₅—(CH₂)_(b)—NR₅— where b is an integer from 1 to 10; R₅            is hydrogen, (C₁-C₄)alkyl, phenyl, naphthyl, tolyl or            benzyl;    -   R₁, R₂, R₃ and R_(3a) are the same or different and each        independently selected from (C₁-C₆)alkyl, (C₁-C₆)perfluoroalkyl,        (C₆-C₈)aryl, (C₆-C₈)perfluoroaryl, (C₆-C₁₀)aralkyl or        (C₆-C₁₀)perfluoroarylperfluoroalkyl; and    -   Ar₁, Ar₂, Ar₃ and Ar_(3a) are the same or different and are        independently of each other selected from phenylene or        naphthalene group optionally substituted with a group selected        from halogen, —OH, (C₁-C₄)alkyl, (C₁-C₄)alkoxy, (C₆-C₁₀)aryl,        (C₆-C₁₀)aryloxy, (C₆-C₁₂)aralkyl and (C₆-C₁₂)aralkyloxy.

In yet another embodiment of this invention, the compound of the formula(IA), (II) or (IIA) encompasses the following:

-   -   L is a linking group selected from:        -   —C(O)O—(CH₂)_(b)—O(CO)—, —C(O)O—(CH₂)_(b)—,            —(CH₂)_(b)—O(CO)—(CH₂)_(b)—, —O—(CH₂)_(b)—O—, —O—(CH₂)_(b)—,            —(CH₂)_(b)—O—(CH₂)_(b)—, —C(O)NR₅—(CH₂)_(b)—NR₅(CO)—,            —NR₅—(CH₂)_(b)—, —(CH₂)_(b)—NR₅—(CH₂)_(b)—,            —NR₅—(CH₂)_(b)—NR₅— where b is an integer from 1 to 6; R₅ is            hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl,            tert-butyl, phenyl, naphthyl, tolyl or benzyl;    -   R₁, R₂, R₃ and R_(3a) are the same or different and each        independently selected from methyl, ethyl, propyl, isopropyl,        n-butyl, tert-butyl, trifluoromethyl, pentafluoroethyl,        heptafluoropropyl, phenyl, pentafluorophenyl, benzyl or        heptafluorobenzyl; and    -   Ar₁, Ar₂, Ar₃ and Ar_(3a) are the same or different and are        independently of each other selected from phenylene or        naphthalene group optionally substituted with a group selected        from fluorine, methyl, ethyl, propyl, isopropyl, n-butyl,        tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy,        tert-butoxy, phenyl, naphthyl, tolyl, benzyl, phenoxy,        naphthyloxy, tolyloxy or benzyloxy.

In yet another embodiment of this invention, the compound of the formula(II) or (IIA) encompasses the following:

-   -   L is a linking group selected from:        -   —C(O)O(CH₂)_(b)—O(CO)—, —C(O)O—(CH₂)_(b)—,            —(CH₂)_(b)—O(CO)—(CH₂)_(b)—, —O—(CH₂)_(b)—O—, —O—(CH₂)_(b)—,            —(CH₂)_(b)—O—(CH₂)_(b)—, —C(O)NR₅—(CH₂)_(b)—NR₅(CO)—,            —NR₅—(CH₂)_(b)—, —(CH₂)_(b)—NR₅—(CH₂)_(b)—,            —NR₅—(CH₂)_(b)—NR₅— where b is an integer from 2 to 6; R₅ is            hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl,            tert-butyl, phenyl, naphthyl, tolyl or benzyl;    -   R₁, R₂, R₃ and R_(3a) are the same or different and each        independently selected from methyl, ethyl, propyl, isopropyl,        n-butyl, tert-butyl, trifluoromethyl, pentafluoroethyl,        heptafluoropropyl, phenyl, pentafluorophenyl, benzyl or        heptafluorobenzyl; and    -   Ar₁, Ar₂, Ar₃ and Ar_(3a) are the same or different and are        independently of each other selected from phenylene or        naphthalene group optionally substituted with a group selected        from fluorine, methyl, ethyl, propyl, isopropyl, n-butyl,        tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy,        tert-butoxy, phenyl, naphthyl, tolyl, benzyl, phenoxy,        naphthyloxy, tolyloxy or benzyloxy.

Non-limiting representative examples of the compounds encompassed by thecompound of formula (IA) may be selected from the group consisting ofthe following:

In a further embodiment the compounds within the scope of compound offormula (I), without any limitation, are selected from the groupconsisting of the following:

In another embodiment, non-limiting examples of the compoundsencompassed by the compound of formula (II) or (IIA) are selected fromthe group consisting of:

In a further embodiment of this invention non-limiting examples ofdiazirine compounds of this invention may be enumerated as follows:

The compounds of this invention can be synthesized by any of theprocedures known to one skilled in the art. Specifically, as notedabove, a few of the compounds of formula (I), and several of thestarting materials used in the preparation of the compounds of thisinvention are known or are themselves commercially available. Thecompounds of this invention and several of the precursor compounds mayalso be prepared by methods used to prepare similar compounds asreported in the literature and as further described herein. See forexample, K. Simonton et al., RadTech e/5, 2006, Technical Proceedings;and H. Mehenni et al., Aust. J. Chem. 2012, 65, 193-201; pertinentportions of all of which are incorporated herein by reference.

More specifically, the compounds disclosed herein can be synthesizedaccording to the following procedures of Schemes 1-2, wherein R₁, R₄ areas defined for formula (I), R₂ is same as R₁, and Ar₁ and Ar₂ are bothphenyl and L is —C(O)O—R₄—O(CO)— in Scheme 1, represented as a compoundof formula (IB). In Scheme 2, L is —R₄—O—R₄—, and all other substituentsare same as in Scheme 1. Similar procedures can be employed forpreparing the compounds of formula (II). In addition, similar proceduresand/or other procedures known in the art can be used to make variousother compounds of formula (I) or (II) where other L, R₃, Ar₁, Ar₂ andAr₃ groups as defined herein are employed.

In Scheme 1, the compound of formula (IA) is reacted with a compound offormula (IV), where X is a halogen (for example chlorine, bromine oriodine) or a leaving group such as mesylate, tosylate, acetate and thelike. This reaction can be carried out by any of the procedures known inthe art. For example, a solution of compound of formula (IA) can bereacted with a compound of formula (IV) where X is iodine in a suitablesolvent in the presence of a suitable base. Suitable solvents includeketone solvents such as acetone or halogenated solvents such asdichloromethane and the like or mixtures in combination thereof.Suitable base include alkaline metal or alkaline earth metal carbonateor bicarbonate, such as sodium carbonate, potassium carbonate orammonium carbonate, and the like. The reaction can be carried out atambient, sub-ambient or super-ambient temperature conditions suitably ina dark or yellow light conditions to ensure that the diazirine group isnot affected. Generally, the reaction temperature can range from about−20° C. to 60° C., but higher temperatures can be employed dependingupon the type of bis-, tris- or tetrakis-diazirines that are being made.

As noted, Scheme 2 further illustrates preparation of the compounds ofthis invention, a compound of formula (IE), where L is a —R₄—O—R₄—.Again, any of the known procedures and/or variations thereof can beemployed to prepare compounds of formula (IE). In Scheme 2, the compoundof formula (IC) is reacted with a compound of formula (ID) undersuitable reaction conditions to form the compound of formula (IE).Typically, such reactions are carried out in the presence of ethersolvents such as tetrahydrofuran (THF) or diethyl ether in the presenceof a suitable base or an alkaline metal to form the alkaline metal saltof the compound of formula (IC) which is then reacted with a compound offormula (ID), where X is a halogen (for example chlorine, bromine oriodine) or a leaving group such as mesylate, tosylate, acetate and thelike. For example, a compound of formula (IC) in a solvent, such as THFcan be reacted with sodium hydride to form the corresponding sodiumsalt, which is then reacted with a compound of formula (ID) where X isbromine to form the compound of formula (IE). This reaction can becarried out at ambient, sub-ambient or super-ambient temperatureconditions suitably in a dark or yellow light conditions to ensure thatthe diazirine group is not affected. Generally, the reaction temperaturecan range from about −20° C. to 120° C.

In a similar manner various other compounds of formula (I) or (II) canbe prepared employing appropriate starting materials and reagents, asone of skill in the art of organic chemistry can appreciate.

As described herein, the compounds of this invention, particularly, thecompounds of formula (I) and (II) are highly effective as carbeneprecursors when exposed to suitable radiation, and are therefore usefulas photo crosslinking agents as further described in detail hereinbelowand illustrated by specific examples hereafter.

Photoimageable Compositions

In another aspect of this invention there is also provided aphotoimageable composition comprising:

a polymer capable of reacting with a carbene to form a carbene insertedproduct;

a compound of the formula (I) or (II):

wherein,

A is a carbon, silicon, oxygen or nitrogen central core moiety;

L is a bond or a divalent linking or a spacer group selected from:

—C(O)O—R₄—OC(O)—, —C(O)O—R₄—, —R₄—OC(O)—R₄—, —C(O)—R₄—OC(O)—, —C(O)—R₄—,—R₄—C(O)—R₄—, —O—R₄—OC(O)—, —O—R₄—O—, —O—R₄—, —R₄—O—R₄—,—C(O)NR₅—R₄—OC(O)—, —C(O)NR₅—R₄—NR₅C(O)—, —C(O)NR₅—R₄—, —R₄—NR₅C(O)—R₄—,—C(O)—R₄—NR₅C(O)—, —NR₅—R₄—OC(O)—, —NR₅—R₄—NR₅C(O)—, —NR₅—R₄—,—R₄—NR₅—R₄—, —NR₅—R₄—NR₅—, —R₄—, and

where each occurrence of R₄ may be the same or different which is adivalent group independently selected from (C₁-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)aryl, (C₆-C₁₂)aryl(C₁-C₁₂)alkyl,(C₆-C₁₀)heteroaryl,(C₆-C₁₀)heteroaryl(C₁-C₁₂)alkyl, —(CH₂—CH₂—O)_(a)—, where a is aninteger from 1 to 10, provided that when R₄ is —(CH₂—CH₂—O)_(a)— thenthe oxygen end of said group is linked only with either carbon orsilicon containing linking group, which are optionally substituted witha group selected from halogen, —OH, (C₁-C₄)alkyl, (C₁-C₄)alkoxy,(C₆-C₁₀)aryl, (C₆-C₁₀)aryloxy, (C₆-C₁₂)aralkyl and (C₆-C₁₂)aralkyloxy;and R₅ is hydrogen, (C₁-C₆)alkyl, (C₆-C₁₀)aryl or (C₆-C₁₀)aralkyl;

R₁, R₂, R₃ and R_(3a) are the same or different and each isindependently selected from (C₁-C₁₂)alkyl, where portions of hydrogen onalkyl are replaced with fluorine, (C₁-C₁₂)perfluoroalkyl, (C₆-C₁₂)aryl,(C₆-C₁₂)aryl(C₁-C₁₂)alkyl, where portions of hydrogen on alkyl arereplaced with fluorine, and (C₆-C₁₂)arylperfluoro(C₁-C₁₂)alkyl; and

Ar₁, Ar₂, Ar₃ and Ar_(3a) are the same or different and each isindependently selected from (C₆-C₁₂)arylene or (C₆-C₁₂)heteroarylenegroup optionally substituted with a group selected from halogen, —OH,(C₁-C₄)alkyl, (C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₂)aryloxy,(C₆-C₁₂)aryl(C₁-C₄)alkyl and (C₆-C₁₂)aryl(C₁-C₄)alkyloxy; and

a carrier solvent.

It should be noted that in this aspect of the invention, any one or moreof the diazirine compounds of formula (I) or (II) as described hereincan be employed without any limitation. It should further be noted thatany one or more of the polymers that is capable of reacting with acarbene formed from the diazirine compounds of formula (I) or (II) canbe used to form the photoimageable compositions of this invention. Thatis, a photoimageable composition containing one or more compounds offormula (I) or (II) is exposed to suitable radiation, the compounds offormula (I) or (II) will then form a highly active carbene, which canreadily insert into OH, NH, CH or olefinic group or any other functionalgroup that may be present in the polymer which allows such insertion ofcarbene to form the corresponding carbene insertion product, thuscausing crosslinking because of the fact that the compounds of formula(I) or (II) have at least two diazirine functional groups. Since thecompositions of this invention always cause crosslinking upon exposureto radiation, the exposed regions are crosslinked and thus become lesssoluble upon exposure, and as a result facilitate forming images whenimagewise exposed using a photo-patternable mask. Accordingly, thecompositions of this invention can be used as “negative tone”compositions to form photolithographic images.

It should also be noted that a variety of other known “carbeneprecursors” can also be used in combination with one or more compoundsof formula (I) or (II) of this invention. Various such carbeneprecursors are known in the art and are specifically disclosed in U.S.Pat. No. 8,530,212, pertinent portions of which are incorporated hereinby reference. Briefly, such carbene precursors include diazo compoundsand their precursors, hydrazones. A variety of diazo- or hydrazonecompounds can be used in combination with the photoimageablecompositions of this invention.

In one of the embodiments the compositions of this invention encompassesa polymer which is capable of forming a cross-linked product uponreaction with a carbene. Any of the polymers that is capable of reactingwith a carbene generated from the compounds of formula (I) or (II) canbe used in the compositions of this invention. Representative examplesof such polymers include natural or synthetic polymers including withoutany limitation a polysaccharide, a polyglycoside, a cellulose, apolypeptide, a protein, a polyester, a polyether, an epoxy resin, apolyacrylate, a polyacrylic, a polymethacrylate, a polycarbonate, apolyketone, polyetheretherketone (PEEK), a polyacetal, a polyamide, apolyetherimide, a polyimide, a polysulfone, a polyolefin, apolystyrenic, a polyvinyl and its copolymer, poly(vinyl chloride) (PVC),a polysilane, a polysiloxane, a polyurea, a polyurethane, polylacticacid, polyvinylidene chloride, a fluoro-polymer, a polyethylene imine ora salt thereof.

In yet another embodiment the polymer that can be employed to form thephotoimageable composition is selected from the group consisting of:

a polycycloolefinic polymer;

a polyacrylate;

polyvinyl butyral, commercially available as BUTACITE® (from DuPont),MOWITAL® (from Kuraray) or BUTVAR® (from Eastman Chemical);

polyvinyl trimethylsilane (PVTMS);

hydrogenated styrenic block copolymer (commercially available as SEPTON®2002 from Kuraray);

ethyl cellulose; and

poly(4-tert-butyl-styrene).

In another embodiment the polymer employed is a polycycloolefinicpolymer. A variety of cyclo olefinic polymers are commercially availableand all of which can be used in the compositions of this invention. Forexample, ZEONEX® (from Nippon Zeon) and TOPAS® (from Topas AdvancedMaterials Inc.) can be used to form the compositions of this invention.

In another embodiment, the compositions of this invention encompasses apolymer which is a polycycloolefinic polymer comprising at least onerepeat unit represented by formula (IIIA), said repeat unit is derivedfrom a monomer of formula (III):

-   -   wherein:    -   denotes a place of bonding with another repeat unit;    -   p is an integer 0, 1 or 2;    -   R₆, R₇, R₈ and R₉ are the same or different and each        independently of one another is selected from hydrogen, linear        or branched (C₁-C₁₆)alkyl, (C₁-C₁₆)alkenyl,        hydroxy(C₁-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl,        (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,        (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, perfluoro(C₆-C₁₀)aryl,        perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl,        di(C₁-C₂)alkylmaleimide(C₃-C₆)alkyl,        di(C₁-C₂)alkylmaleimide(C₂-C₆)alkoxy(C₁-C₂)alkyl, hydroxy,        (C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,        (C₇-C₁₄)tricycloalkoxy, (C₁-C₁₂)alkoxy(C₁-C₈)alkyl,        (C₆-C₁₀)aryloxy(C₁-C₃)alkyl, (C₅-C₁₀)heteroaryloxy(C₁-C₃)alkyl,        (C₆-C₁₀)aryloxy, (C₅-C₁₀)heteroaryloxy, (C₁-C₆)acyloxy,        (C₁-C₆)acyloxy, oxiranyl(C₀-C₈)alkyl,        oxiranyl(CH₂)_(c)O(CH₂)_(d)—, halogen or a group of formula (A):

—(CH₂)_(c)—(OCH₂—CH₂)_(d)—OR  (A)

-   -   wherein:    -   c is an integer 0, 1, 2, 3 or 4;    -   d is an integer 0, 1, 2, 3 or 4; and    -   R is linear or branched (C₁-C₆)alkyl, (C₅-C₈)cycloalkyl,        (C₆-C₁₀)aryl or (C₇-C₁₂)aralkyl; where each of the        aforementioned substituents are optionally substituted with a        group selected from halogen or hydroxy.

In another embodiment of this invention the polymer employed in thecomposition of this invention is a cycloolefinic polymer, wherein thepolymer comprises two or more different repeat units of formula (IIIA).That is the polymer employed is either a copolymer or a terpolymer.

It should further be noted that any of the known monomers of formula(III) can be employed in this aspect of the invention. Representativeexamples of monomers of formula (IV) include the following without anylimitations:

Again, any of the polymerizable monomer as described herein can be used.For example, the polymerizable monomer is selected from the groupconsisting of:

-   bicyclo[2.2.1]hept-2-ene (NB);-   5-butylbicyclo[2.2.1]hept-2-ene (BuNB);-   5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);-   5-octylbicyclo[2.2.1]hept-2-ene (OctNB);-   5-decylbicyclo[2.2.1]hept-2-ene (DecNB);-   5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (1-ButenylNB);-   5-(but-2-en-1-yl)bicyclo[2.2.1]hept-2-ene (2-ButenylNB);-   5-(but-1-en-1-yl)bicyclo[2.2.1]hept-2-ene (3-ButenylNB);-   5-perfluoroethylbicyclo[2.2.1]hept-2-ene (C₂F₅NB);-   5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C₄F₉NB);-   5-perfluorohexylbicyclo[2.2.1]hept-2-ene (C₆F₁₃NB);-   norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);-   1-(3-(bicyclo[2.2.1]hept-5-en-2-yl)propyl)-3,4-dimethyl-1H-pyrrole-2,5-dione    (PrDMMINB);-   1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione    (BuDMMINB);-   1-(6-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)-3,4-dimethyl-1H-pyrrole-2,5-dione    (HexDMMINB);-   5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);-   5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene    (NBTON);-   bicyclo[2.2.1]hept-5-en-2-yl(ethoxy)dimethylsilane (NBSiMe₂(OEt);-   bicyclo[2.2.1]hept-5-en-2-ylmethyl acetate (MeOAcNB); and-   bicyclo[2.2.1]hept-5-en-2-ylmethanol (MeOHNB).

The polymers derived from monomer of formula (III) can generally be madeby a variety of procedures known in the art. For example, by employing atransition metal catalysts, such as palladium or nickel catalyst, thepolymers can be formed by way of vinyl addition polymerizationprocedures, see U.S. Pat. No. 7,799,883, pertinent portions of which isincorporated herein by reference.

In a further embodiment, the composition of this invention encompasses apolymer which is a copolymer of maleic anhydride and at least one repeatunit of formula (IIIA). Such copolymers are generally made by a freeradical polymerization conditions.

In yet a further embodiment, the composition of this inventionencompasses a copolymer of maleic anhydride and a monomer of formula(IIIA) wherein the maleic anhydride ring of the copolymer is at leastpartially opened with an alcohol, see for example U.S. Pat. No.8,715,900, pertinent portions of which are incorporated herein byreference. In another embodiment the compositions of this inventionencompasses a copolymer of maleic anhydride and a monomer of formula(IIIA) wherein the maleic anhydride ring of the copolymer is at leastpartially opened with an amine.

Non-limiting examples of such copolymer include:

a copolymer containing repeating units derived frombicyclo[2.2.1]hept-2-ene and maleic anhydride ring opened withn-butanol; and

a copolymer containing repeating units derived from5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene and maleic anhydride ringopened with n-butanol.

Various other non-limiting examples of polymers that are suitable forforming the compositions of this invention may be selected from thegroup consisting of:

poly(5-hexylbicyclo[2.2.1]hept-2-ene) (poly(HexNB));

poly(5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene) (poly(l-ButenylNB));

poly(5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene) (poly(C₄F₉NB));

a copolymer of bicyclo[2.2.1]hept-2-ene (NB) andbicyclo[2.2.1]hept-5-en-2-yl(ethoxy)dimethylsilane (NBSiMe₂(OEt);

a copolymer of norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol(HFANB) and bicyclo[2.2.1]hept-5-en-2-ylmethanol (MeOHNB); and

a copolymer containing repeating units derived frombicyclo[2.2.1]hept-2-ene and maleic anhydride ring opened withn-butanol.

The polymers employed to form the compositions of this inventiongenerally exhibit a number average molecular weight (M_(w)) of at leastabout 3,000. In another embodiment, the polymer employed in thecomposition of this invention has a M_(w) of at least about 10,000. Inyet another embodiment, the polymer employed in the composition of thisinvention has a M_(w) of at least about 50,000. In some otherembodiments, the polymer of this invention has a M_(w) of at least about100,000. In some other embodiments, the polymer of this invention has aM_(w) ranging from about 100,000 to 500,000. The weight averagemolecular weight (M_(w)) of the polymer can be determined by any of theknown techniques, such as for example, by gel permeation chromatography(GPC) equipped with suitable detector and calibration standards, such asdifferential refractive index detector calibrated withnarrow-distribution polystyrene standards.

As already noted above, the composition of this invention encompassesone or more compounds of formula (I) or (II). As further noted any ofthe compounds as enumerated herein without any limitation can be used informing the compositions of this invention.

Any of the solvents that can dissolve all of the components of thecomposition of this invention can be used as a carrier solvent.Representative examples of such solvents include alcohols, such asethanol, isopropanol, butanols, and the like. Ketone solvents, such asacetone, methyl ethyl ketone (MEK), cyclohexanone, cyclopentanone, andthe like. Hydrocarbon solvents, such as decane, toluene, p-menthane, andthe like. Ester solvents, such as benzyl acetate, ethyl acetate, and thelike. Glycol and ether solvents, such as diethylene glycol dimethylether, propylene glycol monomethyl ether (PGME), propylene glycolmonomethyl ether acetate (PGMEA), and the like. Various other solvents,such as N-methyl-2-pyrrolidone (NMP), gamma-butyrolactone (GBL),N,N-dimethylacetamide, N,N-dimethylformamide (DMF), anisole, methyl3-methoxypropionate, tetrahydrofuran (THF),3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane(HFE-7500), 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane,1,1,1,2,2,3,4,4,4-nonafluoro-3-methoxybutane and mixtures in anycombination thereof.

In another aspect of this invention there is further provided a methodof forming a film for the fabrication of a microelectronic oroptoelectronic device comprising:

coating a suitable substrate with a composition according to thisinvention to form a film;

patterning the film with a mask by exposing to a suitable radiation;

developing the film after exposure to form a photo-pattern; and

curing the film by heating to a suitable temperature.

The coating of the desired substrate to form a film with photosensitivecomposition of this invention can be performed by any of the coatingprocedures as described herein and/or known to one skilled in the art,such as by spin coating. Other suitable coating methods include withoutany limitation spraying, doctor blading, meniscus coating, ink jetcoating and slot coating. Suitable substrate includes any appropriatesubstrate as is, or may be used for electrical, electronic oroptoelectronic devices, for example, a semiconductor substrate, aceramic substrate, a glass substrate.

Next, the coated substrate is first softbaked before the curing, i.e.,heated to facilitate the removal of residual casting solvent, forexample to a temperature from 60° C. to 120° C. for from about 1 to 30minutes, although other appropriate temperatures and times can be used.In some embodiments the substrate is first softbaked before the curingat a temperature of from about 70° C. to about 100° C. for 2 minutes to10 minutes. After the heating, the film is generally imagewise exposedto an appropriate wavelength of actinic radiation, wavelength isgenerally selected based on the choice of the diazirine compound offormula (I) or (II) employed in the polymer composition as describedherein. However, generally such appropriate wavelength is that producedby a mercury vapor lamp which is from 200 to 450 nm depending upon thetype of mercury vapor lamp employed. It will be understood that thephrase “imagewise exposure” means exposing through a masking element toprovide for a resulting pattern of exposed and unexposed portion of thefilm.

After an imagewise exposure of the film formed from the composition inaccordance with the present invention, a development process isemployed. As noted above, the compositions of this invention functionprimarily as “negative tone” compositions, that is, the developmentprocess removes only unexposed portions of the film thus leaving anegative image of the masking layer in the film.

Suitable developers can include aqueous solutions of inorganic alkalissuch as sodium hydroxide, potassium hydroxide, sodium carbonate;ammonia, or aqueous solutions of organic bases such as 0.26 Ntetramethylammonium hydroxide (TMAH), ethylamine, triethylamine andtriethanolamine. Aqueous solutions of TMAH are well known developersolutions in the semiconductor industry. Suitable developers can alsoinclude organic solvents such as PGMEA, 2-heptanone, cyclohexanone,toluene, xylene, ethyl benzene, mesitylene and butyl acetate, amongothers, or mixtures of these solvents in any combination thereof.

Thus some embodiments of the present invention provide self-imageablefilms that after imagewise exposure, a resulting image is developedusing an aqueous base solution, while for other such embodiments aresulting image is developed using an organic solvent. Regardless ofwhich type of developer is employed, after the image is developed, thesubstrate is rinsed to remove excess developer solution, typical rinseagents are water or appropriate alcohols and mixtures thereof.

Accordingly, in some embodiments the developer employed is an aqueousdeveloper which is tetramethylammonium hydroxide (TMAH). In some otherembodiments the developer employed is an organic solvent which isselected from the group consisting of decane, p-menthane,3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane(HFE-7500), and mixtures in any combination thereof.

After the aforementioned rinsing, the substrate is dried and the imagedfilm finally cured. That is to say, the image is fixed. Such reaction isgenerally a further cross-linking reaction that can be initiated byheating and/or non-imagewise blanket exposure of the remaining material.Such exposure and heating can be in separate steps or combined as isfound appropriate for the specific use of the imaged film. The blanketexposure is generally performed using the same energy source as employedin the imagewise exposure although any appropriate energy source can beemployed. The heating is generally carried out at a desirabletemperature, for example, from above 110° C. for a time of from severalminutes to one or more hours. Where the remaining layer has been exposedduring the imagewise exposure, image fixing is generally accomplished bya heating step to be tailored to complete any reaction initiated by theexposure. However an additional blanket exposure and heating, asdiscussed above, can also be employed. It should be realized, however,that the choice of a final cure process is also a function of the typeof device being formed; thus a final fixing of the image may not be afinal cure where the remaining layer is to be used as an adhesive layeror structure.

Accordingly, in some embodiments the resulting imagewise film or layeris cured by heating the patterned and developed substrate at atemperature of from about 120° C. to about 250° C. for about 20 minutesto about 240 minutes. In some other embodiments such curing is carriedout at a temperature of from about 130° C. to about 200° C. for about 30minutes to about 180 minutes. In yet some other embodiments such curingis carried out at a temperature of from about 150° C. to about 180° C.for about 60 minutes to about 120 minutes. Finally, in some otherembodiments of this invention, the curing is performed at a temperatureof from about 130° C. to about 200° C. at an incremental heating ramp ofabout 5° C./minute and for about 1 to 3 hours.

The devices are produced by using embodiments of the alkali solublephotosensitive resin composition of the present invention to form layerswhich are characterized as having high heat resistance, an appropriatewater absorption rate, high transparency, and low permittivity. Inaddition, such layers generally have an advantageous coefficient ofelasticity after curing.

As previously mentioned, exemplary applications for embodiments of thephotosensitive compositions in accordance with the present inventioninclude redistribution layer, die attach adhesive, wafer bondingadhesive, insulation films (interlayer dielectric layers), protectingfilms (passivation layers), mechanical buffer films (stress bufferlayers) or flattening films for a variety of semiconductor devices,printed wiring boards. Specific applications of such embodimentsencompass a die-attach adhesive to form a single or multilayersemiconductor device, dielectric film which is formed on a semiconductordevice; a buffer coat film which is formed on the passivation film; aninterlayer insulation film which is formed over a circuit formed on asemiconductor device.

Advantageously, it has now been found that the photosensitivecompositions of this invention may be useful to form adhesive layers forbonding the semiconductor chips to each other, such as in chip-stackapplications. For example, a redistribution layer used for such apurpose is composed of a cured product of the photosensitive adhesivecomposition of the present invention. Surprisingly, it has now beenfound that although the adhesive layer is a single-layer structure, itnot only exhibits sufficient adhesiveness to the substrate but also isfree of significant stress resulting due to the curing step.Accordingly, it may now be possible to avoid undesirably thick layer offilm encompassing the chip as a laminate. It has been further observedthat the laminates formed in accordance with the present invention arereliable in that the relaxation of stress concentration between layerscaused by thermal expansion difference or the like can be obtained. As aresult, the semiconductor device having low height and high reliabilitycan be obtained. That is, devices with low aspect ratio and lowthickness can be obtained. Such semiconductor device becomesparticularly advantageous to electronic equipment, which has very smallinternal volume and is in use while carrying as a mobile device, forexample. Even more advantageously, by practice of this invention it maynow be possible to form a variety of electronic devices featuringhitherto unachievable level of miniaturization, thinning andlight-weight, and the function of the semiconductor device is not easilydamaged even if such devices are subject to rugged operations such asswinging or dropping.

Accordingly, in some of the embodiments of this invention there is alsoprovided a cured product obtained by curing the photosensitivecomposition as described herein. In another embodiment there is alsoprovided an optoelectronic or microelectronic device comprising thecured product of this invention as described herein.

Advantageously it has also been found that the composition of thisinvention features low dielectric constant, generally less than 3.9, asdescribed herein. Accordingly, in some of the embodiments the curedproduct obtained from the composition of this invention exhibits adielectric constant of 3.6 or less at 1 MHz. In some other embodimentsthe cured product obtained from the composition of this inventionexhibits a dielectric constant of 3.2 or less at 1 MHz. In yet someother embodiments the cured product obtained from the composition ofthis invention exhibits a dielectric constant of 3.0 or less at 1 MHz.

The following examples are detailed descriptions of methods ofpreparation and use of certain compounds/monomers, polymers andcompositions of the present invention. The detailed preparations fallwithin the scope of, and serve to exemplify, the more generallydescribed methods of preparation set forth above. The examples arepresented for illustrative purposes only, and are not intended as arestriction on the scope of the invention. As used in the examples andthroughout the specification the ratio of monomer to catalyst is basedon a mole to mole basis.

This invention is further illustrated by the following examples whichare provided for illustration purposes and in no way limit the scope ofthe present invention.

EXAMPLES

The following abbreviations have been used hereinbefore and hereafter indescribing some of the compounds, instruments and/or methods employed toillustrate certain of the embodiments of this invention:

NB: bicyclo[2.2.1]hept-2-ene; 1-ButenylNB:5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene); NBSiMe₂(OEt):bicyclo[2.2.1]hept-5-en-2-yl(ethoxy)dimethylsilane; MeOAcNB:bicyclo[2.2.1]hept-5-en-2-ylmethyl acetate; MeOHNB:bicyclo[2.2.1]hept-5-en-2-ylmethanol; HFANB:norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol; HexNB:5-hexylbicyclo-[2.2.1]hept-2-ene; C₄F₉NB:5-perfluorobutylbicyclo[2.2.1]hept-2-ene; EPEsNB: ethyl3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoate; NBEtCOOH:3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid; MA: maleic anhydride;NBTON: 5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene;d-IBU: diisobutylene; ROMA: ring opened maleic anhydride copolymer withalcohol; ROME ring opened maleic anhydride copolymer with amine; PGME:propylene glycol methyl ether; PGMEA: propylene glycol methyl etheracetate; EtOAc: ethyl acetate; HFE-7500:3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane;NaH: sodium hydride; DANFABA:N,N-dimethylaniliniumtetrakis(pentafluorophenyl)-borate; LiFABA: lithium(diethyl ether) tetrakis(pentafluorophenyl)borate([Li(OEt₂)_(2.5)][B(C₆F₅)₄]); R.T.—room temperature; LC-MS: liquidchromatography-mass spectroscopy; GPC: gel permeation chromatography;phr: parts per hundred parts of resin.

The following examples describe the procedures used for the preparationof various compounds as disclosed herein including certain of thestarting materials employed in the preparation of the compounds of thisinvention. However, it should be noted that these examples are intendedto illustrate the disclosure without limiting the scope thereof.

Example 1 Propane-1,3-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate)

All of the procedures described herein were carried out under yellowlight conditions. To a 60 mL crimp cap bottle equipped with a stirbarwas added 4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzoic acid (2 g, 8.7mmol, 2.5 equiv., purchased from TCI America), followed by potassiumcarbonate (2.4 g, 17.3 mmol, 5 equiv.) and acetone (20 mL). To thestirring slurry was added diiodopropane (1.1 g, 3.5 mmol, 1 equiv.). Thereaction mixture was allowed to stir for 20 h.

The reaction mixture was then filtered through #4 filter paper followedby dilution with EtOAc (20 mL). The resulting solution was washed withwater (3×10 mL). The organic layer was concentrated to a very smallvolume (0.73 g, 42% recovery). LC-MS analysis of the reaction mixtureindicated formation of two products: the target compound (M+1−2N₂=445)and the mono-iodo byproduct, 3-iodopropyl4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate, (M+1−N₂=371) in a 1:3ratio based on area percent using a UV detector at 254 nm. The mixturewas used without further purification.

Example 23,3′-((oxybis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine)

All of the procedures described herein were carried out in the dark. Toa 60 mL crimp cap bottle equipped with a magnetic stirbar was added NaH(60% dispersion in mineral oil) (0.204 g, 5.1 mmol, 1.1 eq). The bottlewas sealed with a septum cap and a vent needle (20 gauge) was added. THF(7 mL) was syringed into the reactor. The solution of4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl alcohol (1 g, 4.6 mmol,purchased from TCI America) in THF (3 mL) was added slowly to thereactor by syringe (bubbling was visible). This mixture stirred for 10min followed by addition of neat4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl bromide (1.3 g, 4.6 mmol,purchased from TCI America) by syringe. The reaction mixture was allowedto stir at room temperature overnight (20 h).

Water (10 mL) was then added to the reaction slurry resulting in abiphasic mixture. The organic layer was removed from the aqueous layerand washed with water (2×10 mL). The organic layer was concentratedunder vacuum to afford the crude product as a yellow oil/solid mixture.The crude material was placed onto a column of silica gel (3 cm×26 cm)and 25 mL fractions were taken eluting with 10% EtOAc in hexane.Fractions 3 and 4 were combined and concentrated to afford the titlecompound as a yellow oil (1 g). LC-MS showed that the final product was77% pure (M−2N₂=358) based on area percent using a 254 nm detector. ¹HNMR (tetrachloroethane-d₂): 7.45 (d, 4H), 7.25 (d, 4H), 4.61 (s, 2H).¹³C NMR (tetrachloroethane-d₂): 140.02, 128.65, 127.98, 122.25 (q),71.64, 71.44.

B. Polymer Synthesis Examples Polymer Examples

Various polymers as described herein for forming the photoimageablecompositions of this invention were commercially available and were usedas such. The vinyl addition polymers containing the functionalizednorbornene monomers can also be made in accordance with procedures knownin the art. A few of the representative non-limiting examples of suchpolymers are also described hereinbelow.

Example 3 Poly(HexNB)

HexNB (1.6 Kg, 9 moles), cyclohexane (6.2 Kg) and ethyl acetate (3 Kg)were mixed together, nitrogen sparged for 30 minutes and cooled to 20°C. (η⁶-toluene)Ni(C₆F₅)₂ (12.2 g, 0.025 moles) and toluene (250 g) wereadded to the monomer mixture. The reactor temperature was increased to40° C. and the mixture was stirred for 3 hours. Residual catalyst wasremoved and the polymer was precipitated into isopropanol. Afterisolating the polymer by filtration, it was dried in a vacuum oven at80° C. The polymer was characterized by GPC: M_(w): 190,000 M_(n):75,000

Example 4 Copolymer of NB/NBSiMe₂(OEt) (82/18)

Norbornene (60.2 g, 0.64 moles), NBSiMe₂(OEt) (31.4 g, 0.16 moles),cyclohexane (546 g) and ethyl acetate (223 g) were mixed together,nitrogen sparged for 30 minutes and heated to 35° C.(η⁶-toluene)Ni(C₆F₅)₂ (5.54 g, 0.011 moles) and ethyl acetate (50 g)were added to the monomer mixture. The reactor temperature was increasedto 40° C. and the mixture was stirred for 2 hours. Residual catalyst wasremoved and the polymer was precipitated into methanol. After isolatingthe polymer by filtration, it was dried in a vacuum oven at 50° C. Thepolymer was characterized by GPC and ¹H NMR: M_(w): 89,000 M_(n):49,000; composition as determined by ¹H NMR was: 82% norbornene/18%NBSiMe₂(OEt)

Example 5 Copolymer of HFANB/MeOHNB (63/37)

A reactor was charged with HFANB (1.81 Kg, 6.6 moles), MeOAcNB (728 g,4.4 moles), DANFABA (28.8 g, 0.04 moles), formic acid (27.5 g, 0.6moles), and toluene (2000 g). A syringe pump was charged with additionalMeOAcNB (200 g, 1.2 moles). In a dry box the palladium catalyst,palladium(acetylacetonato)(acetonitrile)₂tetrakis(pentafluorophenyl)borate [Pd(acac)(CH₃CN)₂]B(C₆F₅)₄, (11.6 g)was charged to a pressure cylinder. Anhydrous ethyl acetate (132 g) wasadded to the pressure cylinder. The solution in the reactor was heatedto 70° C. under a nitrogen atmosphere. The catalyst solution wastransferred to the heated reaction mixture. Following catalyst injectionthe syringe pump containing MeOAcNB was started and monomer was added tothe reactor according to a predetermined schedule: 0.733 g/min for 28minutes, 0.262 g/min for 78 minutes, 0.190 g/min for 108 minutes, 0.159g/min for 128 minutes, 0.134 g/min for 153 minutes, 0.106 g/min for 194minutes, 0.078 g/min for 264 minutes and 0.068 g/min for 303 minutes. Atthe end of the predetermined schedule any residual MeOAcNB monomer inthe syringe was discarded. The solution was mixed for 22 hours followingcatalyst injection. The polymer solution was cooled to room temperature.Residual catalyst was removed and the acetoxy group of the repeat unitsof MeOAcNB was removed by hydrolysis to form MeOHNB repeat units in thepolymer backbone. The polymer solution was precipitated into heptanesand dried in a vacuum oven at 70° C. The polymer was characterized byGPC and ¹H NMR: M_(w): 3640 M_(n): 2640; composition as determined by ¹HNMR was: 63% HFANB/37% MeOHNB.

Example 6 poly(ButentylNB)

A solution of LiFABA, ([Li(Et₂O)₂₅][B(C₆F₅)₄], (47.4 mg, 0.054 mmol) andbutenylnorbornene (20 g, 136 mmol) in toluene (total solution volume 50mL) was heated to 70° C. Then a solution of [(allyl)palladium(trinaphthylphosphine)(trifluoroacetate)] (9.6 mg, 0.014 mmol, 0.01 M)in toluene was added to the reaction mixture. The reaction mixturestirred for 1 h at 70° C. The reaction mixture was allowed to cool toroom temperature. The reaction mixture was diluted to 100 mL totalvolume with THF and was poured into MeOH (˜10 fold excess). Theprecipitated polymer was filtered, then dried in a vacuum oven at 50° C.overnight to give a white powder. Yield: 18 g, 90%. The polymer wascharacterized by GPC and ¹H NMR: M_(w): 24,800, M_(w)/M_(n): 2.25. Theratio of terminal to isomerized olefins associated with the butenylpendent group was determined by ¹H NMR methods and were found to be 25to 1.

Example 7 Poly(NBC₄F₉)

NBC₄F₉ (62.4 g, 0.2 moles), trifluorotoluene (52.4 g) and toluene (15 g)were mixed together, nitrogen sparged for 30 minutes and heated to 25°C. (η6-toluene)Ni(C₆F₅)₂ (0.97 g, 0.002 moles) and toluene (7.9 g) wereadded to the monomer mixture. The mixture was stirred for 8 hours.Residual catalyst was removed and the polymer was precipitated intomethanol. After isolating the polymer by filtration, it was dried in avacuum oven at 75° C. The polymer was characterized by GPC: M_(w):210,000 M_(n): 150,000.

Example 8 Ring Opened Copolymer of NB/MA with n-BuOH ROMA

Maleic Anhydride (MA, 122.4 g, 1.25 mol), 2-norbornene (NB, 117.6 g,1.25 mol) and dimethyl 2,2′-azobis(2-methylpropionate) (11.5 g, 50 mmol)were dissolved in MEK (150.8 g) and toluene (77.7 g) and charged to anappropriately sized reaction vessel. The solution was sparged withnitrogen for 10 min to remove oxygen and then heated to 60° C. withstirring. After 16 hr, MEK (320 g) was added to the reaction mixture.The resulting solution was added to a suspension of NaOH (12.5 g, 0.31mol), n-BuOH (463.1 g, 6.25 mol) and mixed at 45° C. for 3 hr. Themixture was then cooled to 40° C., treated with 88% formic acid (49 g,0.94 mol) for protonation, and then washed with water three times. Theorganic phase was separated and residual monomer extracted with hexane.After the extraction, PGMEA was added to the reaction mixture and heatedto 120° C. for additional reaction. Samples were removed to monitor thedissolution rate of the polymer and the reaction mixture cooled andsolvent exchanged into PGMEA when the desired dissolution rate wasachieved (˜800 nm/sec in 0.26 N TMAH). The ring-opened polymer as a 20wt % solution was obtained (1107.7 g). The polymer was characterized byGPC: M_(w): 13,700, M_(n): 7,400). The polymer solution was heated to120° C. in a stainless steel reactor. Aliquots of the reaction mixturewere taken over time and the dissolution rate of this polymer in 0.26 NTMAH was determined (see Table 1). After 5 hours the desired dissolutionrate was achieved and the reactor was cooled. The solution wasconcentrated by rotoevaporation until a solids content of −21% wasreached. The polymer was characterized by GPC: M_(w): 11,600, M_(n):5,630.

TABLE 1 Reaction time Dissolution rate (hours) (nm/sec) 0 705 2 380 4298 5 213

Example 8A Ring Opened Copolymer of NB/MA with n-BuOH ROMA

Example 8 was substantially repeated in this Example 8a to obtain apolymer having M_(w) of 11,600.

Example 8B Copolymer of HFANB/NBEtCOOH (75/25)

A reactor was charged with HFANB (4.9 kg, 17 moles), EPEsNB (0.58 kg,3.1 moles), toluene (18.4 kg) and DME (2.4 kg). A pressure cylinder wascharged with additional EPEsNB (0.58 kg, 3.1 moles) and toluene (2.6kg). In a dry box (η⁶-toluene)Ni(C₆F₅)₂ (116 g) was charged to apressure cylinder. Anhydrous toluene (1 kg) was airlessly added to thepressure cylinder. The solution in the reactor was sparged with nitrogenfor 15 minutes and then heated to 50° C. The (η⁶-toluene)Ni(C₆F₅)₂solution was transferred to the heated reaction mixture at a rate of 194g/min for 15 minutes. At the end of the predetermined schedule anyresidual EPEsNB/toluene mixture in the pressure cylinder was discarded.The solution was mixed for 22 hours following catalyst injection. Thepolymer solution was cooled to room temperature. Residual catalyst wasremoved and the EPEsNB was deprotected to obtain the title polymer. Thepolymer solution was solvent exchanged into PGME and characterized byGPC: M_(w) 130,000 M_(n) 54,000.

Example 8C d-IBU/NBTON/MA Terpolymer Ring Opened with n-Octyl Amine(ROMI Polymer)

d-IBU/NBTON/MA polymer (192 g) was dissolved in PGMEA (356 g) to obtain35% (w/w) solution. Part of this polymer solution (250 g) wastransferred to a 0.5 L glass reactor equipped with a mechanical stirrer,nitrogen inlet and a port connected to a syringe pump. The solution wassparged with nitrogen and kept under a 20 psig nitrogen blanket andheated to 50° C. while stirring. A solution of 1-octylamine (30 g) wasmade in PGMEA (30 g) and transferred to a stainless-steel syringe. 55 mLof this amine solution (46.4 g) was added to the polymer solution in thereactor at 0.5 mL/min rate using a syringe pump. After amine additionwas complete the reaction mixture was heated to 90° C. for 4 hours whilestirring. The resulting amine treated polymer was withdrawn from thereactor after allowing it to cool to 25° C. The resulting polymer wascharacterized by GPC: M_(w) of 26,600 (PDI 1.8). The acid number of theproduct was 118 mg KOH/g.

Small aliquot (5 g) of the product was added to n-heptane (40 g) whilestirring to separate the solid polymer by precipitation. The solidobtained was washed with n-heptane (20 g) and dried at 80° C. for 24hours in a vacuum oven to obtain 2 g of the solid polymer (100% isolatedyield). The FT-IR analysis of the solid indicated the presence ofcarboxylic acid group (broad peak at 2000-3500 cm⁻¹).

Example 8D Poly(DecNB)

DecNB (290 g, 1.2 moles), cyclohexane (1.1 Kg) and anhydrous ethylacetate (0.53 Kg) were mixed together, nitrogen sparged for 30 minutesand cooled to 20° C. (η⁶-toluene)Ni(C₆F₅)₂ (1.9 g, 0.004 moles) andanhydrous ethyl acetate (17 g) were added to the monomer mixture. Thereactor temperature was increased to 40° C. and the mixture was stirredfor 2 hours. Residual catalyst was removed and the polymer wasprecipitated into isopropanol. After isolating the polymer byfiltration, it was dried in a vacuum oven at 80° C. M_(w): 170,000M_(n): 94,000

Photoimageable Polymer Composition and Imaging Studies

The following Examples illustrate the photocrosslinking and imageabilityof the compounds of this invention with a variety of polymers asdescribed herein.

Example 9 Formulation and Imaging of Polymer of Example 6 UsingBis(diazirine) of Example 1

Polymer from Example 1, poly(butenylNB), (1 g) and bis(diazirine) ofExample 1 (0.73 g) were dissolved in 9 g decane/benzyl acetate (90/10)by rolling the mixture overnight. The solution (3 g) was then dispensedonto a 4 inch thermal oxide silicon wafer. The wafer was spun at 300 rpmfor 40 sec and post apply baked at 120° C. for 2 min. The film thicknesswas determined using a Dektak profilometer and was found to be 0.7 μm.

The film on the silicon wafer was image-wise exposed through a 365 nmband pass filter using an ABM mask aligner and at exposure dose of 967mJ/cm². The film was developed using decane as the solvent for 10seconds. The quality of the resulting 3D relief images were determinedby inspection of the wafer under a microscope. The contact holeresolution was determined to be 10 μm.

Examples 10-24 Formulation and Imaging of Various Polymers UsingBis(diazirine) of Example 2

In each of Examples 10-24, the polymer compositions were prepared as setforth below.

In Example 10, polymer from Example 3, poly(HexNB), (0.55 g) andbis(diazirine) of Example 2 (0.11 g) were dissolved in 5 g decane afterrolling overnight. This solution (2.5 g was further diluted with a 2.5 gof a 10% solution of polymer of Example 3 in decane to give a 10%solution of polymer of Example 3 with 10 phr bis(diazirine) of Example 2(10 parts per hundred parts of the polymer of Example 3).

In Example 11, bis(diazirine) of Example 2 (0.1 g) was added to a 10%solution of ZEONEX® 480R (available from Nippon Zeon) in p-menthane (10g). The resulting mixture was rolled overnight.

In Example 12, a 10% solution of TOPAS® 6013S-04 (available from TopasAdvanced Polymers) in p-menthane and 10 phr bis(diazirine) of Example 2was prepared.

In Example 13, bis(diazirine) of Example 2 (0.1 g) was added to asolution of the polymer from Example 4, copolymer of NB/NBSiMe₂(OEt), (1g) in p-menthane (9 g).

In Example 14, poly(4-t-butyl)styrene (available from Monomer Polymerand Dajac Labs, 1 g) was dissolved in 4 g of p-menthane. To thissolution was added 0.1 g of bis(diazirine) of Example 2.

In Example 15, bis(diazirine) of Example 2 (0.1 g) was added to asolution of the polymer of Example 5, copolymer of HFANB/MeOHNB, inisopropanol (0.92 g of polymer in 5 g of isopropanol).

In Example 16, 0.33 g of a solution of polymer from Example 7,poly(NBC₄F₉), (1 g in 8 g of HFE-7500) was diluted with 2.64 g ofHFE-7500. This solution was mixed with a solution 0.1 g ofbis(diazirine) of Example 2 in 0.9 g of HFE-7500.

In Example 17, bis(diazirine) of Example 2 (0.34 g) was added to thepolymer solution from Example 8 (5 g, approximately 1 g of polymer ofExample 8 in 4 g of PGMEA).

Similarly, Examples 18 to Examples 24 were prepared using the solventsas follows: Example 18 in PGMEA, Example 19 in PGMEA, Example 20 in CPN,Examples 21 and 22 in PGMEA, Example 23 in IPA and Example 24 in decane.

In each of the Examples 10-24, the solution (3 g) was filtered through a0.2 μm PTFE syringe filter onto a 4 inch thermal oxide silicon wafer.

In each of the Examples 10-24, the solution (3 g) dispensed onto a 4inch thermal oxide silicon wafer was spun at 500 rpm for 40 sec thenpost apply baked at 80° C. for 2 min. The film thickness was determinedusing a Dektak profilometer, the film thickness, FT in μm is summarizedin Table 2 for each of these Examples.

In each of the Examples 10-24, the film on the silicon wafer thus formedwas then image-wise exposed through a 365 nm band pass filter using anABM mask aligner. The exposure dose used in each of these Examples aredifferent depending upon the nature of the polymer employed to obtaindesirable resolution of the images formed, and are summarized in Table2.

It is evident from the data presented in Table 2, the degree ofcrosslinking with the polymer and the diazirine of this inventionresults in the observed image resolution. That is, higher thecrosslinking between the polymer and diazirine, higher the imageresolution. The film was developed using various solvents as summarizedin Table 2.

TABLE 2 Exp. FT Example Polymer Dose Develop CH loss No. Example No.M_(w) Solvent FT (mJ/cm²) Conditions resol (%) 10 Example 3 190,000 D1.18 255 30 sec  7 μm 7.6 D 11 Zeonex 480  133,000* PM 1.36 967 30 sec10 μm 12 PM 12 Topas  205,000* PM 1.31 967 20 sec 15 μm 1.5 6013S-04 PM13 Example 4  89,000 PM 2.06 644 30 sec 10 μm 7.6 PM/D 14 p(4-t-Bu-105,000 PM 1.62 967 20 sec 40 μm 40 styrene) PM 15 Example 5  3,640 IPA2.23 644 120 sec  20 μm 0 TMAH 16 Example 7 210,000 HFE- 1.75 791 10 sec80 μm 29 7500 HFE-7500 17 Example 8  13,700 PGMEA 0.88 967 10 sec 10 μm27 TMAH 18  Example 8a  11,600 PGMEA 0.82 405 2 + 2 sec  5 μm 30 HMDSTMAH 19  Example 8b 130,000 PGMEA 1.84 255 2 + 2 sec 10 μm 5 HMDS TMAH20 Poly(isobutyl- CPN 1.81 405 10 + 10 sec 10 μm 16 methacrylate) TMAH21  Example 8c  26,600 PGMEA 0.7 510  2 sec  7 μm 28 TMAH 22  Example 8c 26,600 PGMEA 0.7 967  2 sec 15 μm 0 TMAH 23 Example 5  3,640 IPA 0.44113 60 sec  5 μm 16 TMAH 24  Example 8d 169,000 D 1 510 3 × 10 sec  7 μm3 D *GPC in cyclohexane; FT = film thickness; Exp. dose = exposure doseat 365 nm; D = decane; PM = p-menthane; IPA = isopropanol; HFE-7500:3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane;PGMEA: propylene glycol methyl ether acetate; HMDS: hexamethyldisilane;CPN: cyclopentane; TMAH = 0.26N aqueous tetramethyl ammonium hydroxide.CH resol = contact hole resolution.

As further summarized in Table 2, the time needed to develop the imagesdepended on the type of polymer employed. The quality of the resulting3D relief images were determined by inspection of the wafer under amicroscope.

Now turning to FIG. 1, which shows a photolithograph of the developedsilicon wafer from Example 10, which clearly shows that thebis(diazirine) compounds of this invention are very effective in formingthe crosslinked polymers as apparent from the image resolution of thecontact holes at 7 μm. Similarly, the FIGS. 2 to 4 show photolithographsof various other polymer compositions formed from the diazirines of thisinvention, all of which show similar image resolutions.

COMPARATIVE EXAMPLES

The following Comparative Examples 1 and 2 are provided to show thebis(diazirines) of this invention exhibit superior properties whencompared with similar photocrosslinking agents reported in theliterature. For example, it has been reported that certain of the azidecompounds upon photo exposure provides a nitrene intermediate which canbe used as a crosslinking agent. Comparative Example 1 shows that use ofsuch bis-diazide compound failed to provide similar photocrosslinkingeffect as demonstrated by the bis(diazirine) compounds of thisinvention. The bis-azide compound,(2E,6E)-2,6-bis(4-azidobenzylidene)-4-ethylcyclohexanone was used inComparative Example 1, which is also known as BAC-E of the formula:

Comparative Example 1 Formulation and Imaging of Polymer of Example 3with BAC-E

The polymer of Example 3, poly(hexylNB), (1.29 g) was dissolved in 11.65g of decane. To this solution was added 0.065 g of BAC-E in 1.3 gtoluene. 5.0 g of this formulation was diluted with 4.5 g decane and 0.5g of toluene.

The solution (3 g) was filtered through a 0.45 μm PTFE syringe filteronto a 4 inch thermal oxide silicon wafer. The wafer was spun at 300 rpmfor 40 sec then post apply baked at 120° C. for 2 min. The filmthickness was determined using a Dektak profilometer and was found to be0.5 μm.

The film on the silicon wafer was image-wise exposed through a 365 nmband pass filter using an ABM mask aligner at an exposure dose of 1000mJ/cm². The exposed film was developed in decane for 15 seconds. Thequality of the resulting 3D relief images were determined by inspectionof the wafer under a microscope, no images were observed as the entirefilm had dissolved during develop, thus demonstrating that nophotocrosslinking took place under these conditions.

Comparative Example 2 Imaging of Polymer of Example 6 without Additives

The polymer from Example 6, poly(butenylNB), (1 g) was dissolved in 9 gdecane:benzyl acetate (90:10). The solution (3 g) was deposited onto a 4inch thermal oxide silicon wafer. The wafer was spun at 300 rpm for 40sec then post apply baked at 120° C. for 2 min. The film on the siliconwafer was image-wise exposed through a 365 nm band pass filter at anexposure dose of 967 mJ/cm² using an ABM mask aligner. The film wasdeveloped 10 sec with decane at 50 rpm with 1000 rpm ramp then spun dryat 2000 rpm for 30 sec. The film completely dissolved after development.

Comparative Example 2 again demonstrates that an activephotocrosslinking agent is needed to obtain crosslinked polymer uponexposure to suitable radiation.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A compound of the formula (IA), (II) or (IIA):

wherein, A is a carbon, silicon, oxygen or nitrogen central core moiety;L is a bond or a divalent linking or a spacer group selected from:—C(O)O—R₄—OC(O)—, —C(O)O—R₄—, —R₄—OC(O)—R₄—, —C(O)—R₄—OC(O)—, —C(O)—R₄—,—R₄—C(O)—R₄—, —O—R₄—OC(O)—, —O—R₄—O—, —O—R₄—, —R₄—O—R₄—,—C(O)NR₅—R₄—OC(O)—, —C(O)NR₅—R₄—NR₅C(O)—, —C(O)NR₅—R₄—, —R₄—NR₅C(O)—R₄—,—C(O)—R₄—NR₅C(O)—, —NR₅—R₄—OC(O)—, —NR₅—R₄—NR₅C(O)—, —NR₅—R₄—,—R₄—NR₅—R₄—, —NR₅—R₄—NR₅—, —R₄—, and

 where each occurrence of R₄ may be the same or different which is adivalent group independently selected from (C₁-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)aryl, (C₆-C₁₂)aryl(C₁-C₁₂)alkyl,(C₆-C₁₀)heteroaryl, (C₆-C₁₀)heteroaryl(C₁-C₁₂)alkyl, —(CH₂—CH₂—O)_(a)—,where a is an integer from 1 to 10, provided that when R₄ is—(CH₂—CH₂—O)_(a)— then the oxygen end of said group is linked only witheither carbon or silicon containing linking group, which are optionallysubstituted with a group selected from halogen, —OH, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₀)aryloxy, (C₆-C₁₂)aralkyl and(C₆-C₁₂)aralkyloxy; and R₅ is hydrogen, (C₁-C₆)alkyl, (C₆-C₁₀)aryl or(C₆-C₁₀)aralkyl; R₁, R₂, R₃ and R_(3a) are the same or different andeach is independently selected from (C₁-C₁₂)alkyl, where portions ofhydrogen on alkyl are replaced with fluorine, (C₁-C₁₂)perfluoroalkyl,(C₆-C₁₂)aryl, (C₆-C₁₂)aryl(C₁-C₁₂)alkyl, where portions of hydrogen onalkyl are replaced with fluorine, and(C₆-C₁₂)arylperfluoro(C₁-C₁₂)alkyl; and Ar₁, Ar₂, Ar₃ and Ar_(3a) arethe same or different and each is independently selected from(C₆-C₁₂)arylene or (C₆-C₁₂)heteroarylene group optionally substitutedwith a group selected from halogen, —OH, (C₁-C₄)alkyl, (C₁-C₄)alkoxy,(C₆-C₁₀)aryl, (C₆-C₁₂)aryloxy, (C₆-C₁₂)aryl(C₁-C₄)alkyl and(C₆-C₁₂)aryl(C₁-C₄)alkyloxy; and with the proviso that the followingcompounds are excluded:

where n is 7 or 12; and

where n is 3 or
 5. 2. The compound according to claim 1, which is of theformula (IA), wherein: L is a linking group selected from:—C(O)O—(CH₂)_(b)—O(CO)—, —C(O)O—(CH₂)_(b)—, —(CH₂)_(b)—O(CO)—(CH₂)_(b)—,—C(O)—(CH₂)_(b)—O(CO)—, —C(O)—(CH₂)_(b)—, —(CH₂)_(b)—(CO)—(CH₂)_(b)—,—O—(CH₂)_(b)—O(CO)—, —O—(CH₂)_(b)—O—, —O—(CH₂)_(b)—,—(CH₂)_(b)—O—(CH₂)_(b)—, —C(O)NR₅—(CH₂)_(b)—O(CO)—,—C(O)NR₅—(CH₂)_(b)—NR₅(CO)—, —C(O)NR₅—(CH₂)_(b)—,—(CH₂)_(b)—NR₅(CO)—(CH₂)_(b)—, —C(O)—(CH₂)_(b)—NR₅(CO)—,—NR₅—(CH₂)_(b)—O(CO)—, —NR₅—(CH₂)_(b)—NR₅(CO)—, —NR₅—(CH₂)_(b)—,—(CH₂)_(b)—NR₅—(CH₂)_(b)—, —NR₅—(CH₂)_(b)—NR₅— where b is an integerfrom 1 to 12; R₅ is hydrogen, (C₁-C₄)alkyl, phenyl, naphthyl, tolyl orbenzyl; R₁, R₂, R₃ and R_(3a) are the same or different and eachindependently selected from (C₁-C₆)alkyl, (C₁-C₆)perfluoroalkyl,(C₆-C₈)aryl, (C₆-C₈)perfluoroaryl, (C₆-C₁₀)aralkyl or(C₆-C₁₀)perfluoroarylperfluoroalkyl; and Ar₁, Ar₂, Ar₃ and Ar_(3a) arethe same or different and are independently of each other selected fromphenylene or naphthalene group optionally substituted with a groupselected from halogen, —OH, (C₁-C₄)alkyl, (C₁-C₄)alkoxy, (C₆-C₁₀)aryl,(C₆-C₁₀)aryloxy, (C₆-C₁₂)aralkyl and (C₆-C₁₂)aralkyloxy.
 3. The compoundaccording to claim 2, wherein: L is a linking group selected from:—C(O)O—(CH₂)_(b)—O(CO)—, —C(O)O—(CH₂)_(b)—, —(CH₂)_(b)—O(CO)—(CH₂)_(b)—,—O—(CH₂)_(b)—O—, —O—(CH₂)_(b)—, —(CH₂)_(b)—O—(CH₂)_(b)—,—C(O)NR₅—(CH₂)_(b)—NR₅(CO)—, —NR₅—(CH₂)_(b)—, —(CH₂)_(b)—NR₅—(CH₂)_(b)—,—NR₅—(CH₂)_(b)—NR₅— where b is an integer from 1 to 6; R₅ is hydrogen,methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, phenyl, naphthyl,tolyl or benzyl; R₁, R₂, R₃ and R_(3a) are the same or different andeach independently selected from methyl, ethyl, propyl, isopropyl,n-butyl, tert-butyl, trifluoromethyl, pentafluoroethyl,heptafluoropropyl, phenyl, pentafluorophenyl, benzyl orheptafluorobenzyl; and Ar₁, Ar₂, Ar₃ and Ar_(3a) are the same ordifferent and are independently of each other selected from phenylene ornaphthalene group optionally substituted with a group selected fromfluorine, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl,methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, phenyl,naphthyl, tolyl, benzyl, phenoxy, naphthyloxy, tolyloxy or benzyloxy. 4.The compound according to claim 1, which is selected from the groupconsisting of: methylenebis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate); ethane-1,2-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate); butane-1,4-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);3,3′-((oxybis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine);3,3′-((oxybis(ethane-2,1-diyl))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine);3-(trifluoromethyl)-3-(4-(3-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)propyl)phenyl)-3H-diazirine;3-(trifluoromethyl)-3-(4-(2-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)ethyl)phenyl)-3H-diazirine;4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate;4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenethyl2-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)acetate;2-oxo-2-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)ethyl3-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate;1,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)propan-1-one;1,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)propan-2-one;(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)methyl3-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate;1,2-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)ethane;3-(trifluoromethyl)-3-(4-(3-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)propyl)phenyl)-3H-diazirine;(N-methyl-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido)methyl4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate;N,N′-methylenebis(N-methyl-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamide);2-ethyl-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)oxy)methyl)propane-1,3-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);2-(perfluoroethyl)-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)oxy)methyl)propane-1,3-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);3,3′-((((2-ethyl-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine);and3,3′-(2-(perfluoroethyl)-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine).5. A photoimageable composition comprising: a polymer capable ofreacting with a carbene to form a carbene inserted product; a compoundof the formula (IA), (II) or (IIA):

wherein, A is a carbon, silicon, oxygen or nitrogen central core moiety;L is a bond or a divalent linking or a spacer group selected from:—C(O)O—R₄—OC(O)—, —C(O)O—R₄—, —R₄—OC(O)—R₄—, —C(O)—R₄—OC(O)—, —C(O)—R₄—,—R₄—C(O)—R₄—, —O—R₄—OC(O)—, —O—R₄—O—, —O—R₄—, —R₄—O—R₄—,—C(O)NR₅—R₄—OC(O)—, —C(O)NR₅—R₄—NR₅C(O)—, —C(O)NR₅—R₄—, —R₄—NR₅C(O)—R₄—,—C(O)—R₄—NR₅C(O)—, —NR₅—R₄—OC(O)—, —NR₅—R₄—NR₅C(O)—, —NR₅—R₄—,—R₄—NR₅—R₄—, —NR₅—R₄—NR₅—, —R₄—, and

 where each occurrence of R₄ may be the same or different which is adivalent group independently selected from (C₁-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)aryl, (C₆-C₁₂)aryl(C₁-C₁₂)alkyl,(C₆-C₁₀)heteroaryl, (C₆-C₁₀)heteroaryl(C₁-C₁₂)alkyl, —(CH₂—CH₂—O)_(a)—,where a is an integer from 1 to 10, provided that when R₄ is—(CH₂—CH₂-0)_(a)— then the oxygen end of said group is linked only witheither carbon or silicon containing linking group, which are optionallysubstituted with a group selected from halogen, —OH, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₆-C₁₀)aryl, (C₆-C₁₀)aryloxy, (C₆-C₁₂)aralkyl and(C₆-C₁₂)aralkyloxy; and R₅ is hydrogen, (C₁-C₆)alkyl, (C₆-C₁₀)aryl or(C₆-C₁₀)aralkyl; R₁, R₂, R₃ and R_(3a) are the same or different andeach is independently selected from (C₁-C₁₂)alkyl, where portions ofhydrogen on alkyl are replaced with fluorine, (C₁-C₁₂)perfluoroalkyl,(C₆-C₁₂)aryl, (C₆-C₁₂)aryl(C₁-C₁₂)alkyl, where portions of hydrogen onalkyl are replaced with fluorine, and(C₆-C₁₂)arylperfluoro(C₁-C₁₂)alkyl; and Ar₁, Ar₂, Ar₃ and Ar_(3a) arethe same or different and each is independently selected from(C₆-C₁₂)arylene or (C₆-C₁₂)heteroarylene group optionally substitutedwith a group selected from halogen, —OH, (C₁-C₄)alkyl, (C₁-C₄)alkoxy,(C₆-C₁₀)aryl, (C₆-C₁₂)aryloxy, (C₆-C₁₂)aryl(C₁-C₄)alkyl and(C₆-C₁₂)aryl(C₁-C₄)alkyloxy; and a carrier solvent.
 6. The compositionof claim 5, wherein the polymer is selected from the group consistingof: a polycycloolefinic polymer; a polyacrylate; polyvinyl butyral;polyvinyl trimethylsilane (PVTMS); hydrogenated styrenic blockcopolymer; ethyl cellulose; and poly(4-tert-butyl-styrene).
 7. Thecomposition of claim 5, wherein the polymer is a polycycloolefinicpolymer comprising at least one repeat unit represented by formula(IIIA), said repeat unit is derived from a monomer of formula (III):

wherein:

denotes a place of bonding with another repeat unit; p is an integer 0,1 or 2; R₆, R₇, R₈ and R₉ are the same or different and eachindependently of one another is selected from hydrogen, linear orbranched (C₁-C₁₆)alkyl, (C₁-C₁₆)alkenyl, hydroxy(C₁-C₁₆)alkyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl,perfluoro(C₆-C₁₀)aryl, perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl,di(C₁-C₂)alkylmaleimide(C₃-C₆)alkyl,di(C₁-C₂)alkylmaleimide(C₂-C₆)alkoxy(C₁-C₂)alkyl, hydroxy,(C₁-C₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₁-C₁₂)alkoxy(C₁-C₈)alkyl,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl, (C₅-C₁₀)heteroaryloxy(C₁-C₃)alkyl,(C₆-C₁₀)aryloxy, (C₅-C₁₀)heteroaryloxy, (C₁-C₆)acyloxy, (C₁-C₆)acyloxy,oxiranyl(C₀-C₈)alkyl, oxiranyl(CH₂)_(c)O(CH₂)_(d)—, halogen or a groupof formula (A):(CH₂)_(c)—(OCH₂—CH₂)_(d)—OR  (A) wherein: c is an integer 0, 1, 2, 3 or4; d is an integer 0, 1, 2, 3 or 4; and R is linear or branched(C₁-C₆)alkyl, (C₅-C₈)cycloalkyl, (C₆-C₁₀)aryl or (C₇-C₁₂)aralkyl; whereeach of the aforementioned substituents are optionally substituted witha group selected from halogen or hydroxy.
 8. The composition of claim 7,wherein the polymer comprises one or more repeat units derived from thecorresponding monomers selected from the group consisting of:bicyclo[2.2.1]hept-2-ene (NB); 5-butylbicyclo[2.2.1]hept-2-ene (BuNB);5-hexylbicyclo[2.2.1]hept-2-ene (HexNB); 5-octylbicyclo[2.2.1]hept-2-ene(OctNB); 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (1-ButenylNB);5-(but-2-en-1-yl)bicyclo[2.2.1]hept-2-ene (2-ButenylNB);5-(but-1-en-1-yl)bicyclo[2.2.1]hept-2-ene (3-ButenylNB);5-perfluoroethylbicyclo[2.2.1]hept-2-ene (C₂F₅NB);5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C₄F₉NB);5-perfluorohexylbicyclo[2.2.1]hept-2-ene (C₆F₉NB);norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);1-(3-(bicyclo[2.2.1]hept-5-en-2-yl)propyl)-3,4-dimethyl-1H-pyrrole-2,5-dione(PrDMMINB);1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione(BuDMMINB);1-(6-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)-3,4-dimethyl-1H-pyrrole-2,5-dione(HexDMMINB); 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene (NBTON);bicyclo[2.2.1]hept-5-en-2-yl(ethoxy)dimethylsilane (NBSiMe₂(OEt);bicyclo[2.2.1]hept-5-en-2-ylmethyl acetate (MeOAcNB); andbicyclo[2.2.1]hept-5-en-2-ylmethanol (MeOHNB).
 9. The composition ofclaim 5, wherein the polymer is a copolymer of maleic anhydride and atleast one repeat unit of formula (IIIA).
 10. The composition of claim 9,wherein the maleic anhydride ring of the copolymer is at least partiallyopened with an alcohol.
 11. The composition of claim 10, wherein thepolymer is selected from the group consisting of: a copolymer containingrepeating units derived from bicyclo[2.2.1]hept-2-ene and maleicanhydride ring opened with n-butanol; and a copolymer containingrepeating units derived from 5-n-perfluorobutylbicyclo[2.2.1]hept-2-eneand maleic anhydride ring opened with n-butanol.
 12. The composition ofclaim 7, wherein the polymer is selected from the group consisting of:poly(5-hexylbicyclo[2.2.1]hept-2-ene) (poly(HexNB));poly(5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene) (poly(1-ButenylNB));poly(5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene) (poly(C₄F₉NB)); acopolymer of bicyclo[2.2.1]hept-2-ene (NB) andbicyclo[2.2.1]hept-5-en-2-yl(ethoxy)dimethylsilane (NBSiMe₂(OEt); acopolymer of norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol(HFANB) and bicyclo[2.2.1]hept-5-en-2-ylmethanol (MeOHNB); and acopolymer containing repeating units derived frombicyclo[2.2.1]hept-2-ene and maleic anhydride ring opened withn-butanol.
 13. The composition of claim 5 comprising the compound offormula (IA), which is selected from the group consisting of: methylenebis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate); ethane-1,2-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate); propane-1,3-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate); butane-1,4-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);3,3′-((oxybis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine);3,3′-((oxybis(ethane-2,1-diyl))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine);3-(trifluoromethyl)-3-(4-(3-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)propyl)phenyl)-3H-diazirine;3-(trifluoromethyl)-3-(4-(2-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)ethyl)phenyl)-3H-diazirine;4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate;4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenethyl2-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)acetate;2-oxo-2-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)ethyl3-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate;1,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)propan-1-one;1,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)propan-2-one;(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)methyl3-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate;1,2-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)ethane;3-(trifluoromethyl)-3-(4-(3-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)propyl)phenyl)-3H-diazirine;(N-methyl-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido)methyl4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate; andN,N′-methylenebis(N-methyl-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamide).14. The composition of claim 5 comprising the compound of formula (II)or (IIA), which is selected from the group consisting of:2-ethyl-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)oxy)methyl)propane-1,3-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);2-(perfluoroethyl)-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)oxy)methyl)propane-1,3-diylbis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);3,3′-((((2-ethyl-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine);and3,3′-(((2-(perfluoroethyl)-2-4(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine).15. The composition of claim 5 wherein said carrier solvent is selectedfrom the group consisting of: ethanol, isopropanol, acetone,cyclohexanone, cyclopentanone, decane, toluene, p-menthane, benzylacetate, diethylene glycol dimethyl ether, propylene glycol monomethylether (PGME), propylene glycol monomethyl ether acetate (PGMEA),N-methyl-2-pyrrolidone (NMP), gamma-butyrolactone (GBL),N,N-dimethylacetamide, N,N-dimethylformamide, anisole, methyl3-methoxypropionate, tetrahydrofuran (THF),3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane(HFE-7500), 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane,1,1,1,2,2,3,4,4,4-nonafluoro-3-methoxybutane and mixtures in anycombination thereof.
 16. A method of forming a film for the fabricationof a microelectronic or optoelectronic device comprising: coating asuitable substrate with a composition according to claim 5 to form afilm; patterning the film with a mask by exposing to a suitableradiation; developing the film after exposure to form a photo-pattern;and curing the film by heating to a suitable temperature.
 17. The methodof claim 16, where said developing is performed by an aqueous developer.18. The method of claim 16, where said developing is performed by asolvent.
 19. The method of claim 16, where the substrate is firstsoftbaked before said curing at a temperature of from about 70° C. toabout 130° C. for 2 minutes to 10 minutes.
 20. The method of claim 16,where said curing is performed at a temperature of from about 120° C. toabout 250° C. for about 20 minutes to about 180 minutes.
 21. A curedproduct obtained by curing the composition of claim
 5. 22. Anoptoelectronic or microelectronic device comprising the cured product ofclaim 21.